Natalie's parents separated early in her childhood and she took it badly. She lived with her mother Andrea Price in Walford, but she had been closer to her father, Dave, and missed him terribly. Andrea favoured her other children, especially her older daughter Susie, over Natalie. She was highly critical of Natalie and blamed her for the breakdown of her marriage (the unwanted pregnancy had ruined her figure and singing career, causing her husband to leave her). Andrea and Susie ridiculed Natalie for missing her father and wanting to keep in touch; Andrea claimed that Dave had no interest in Natalie.
At age 11 when she was in secondary school, Natalie met Bianca Jackson. They became friends, but Bianca often sidelined her in favour of Tiffany Raymond, whom Bianca treated with more respect than Natalie. In fact, Tiffany joined Bianca in teasing Natalie. Natalie resented Tiffany and was pleased when she moved away after leaving school at 16 in 1993.
Mischievous Natalie arrived in Walford in January 1994. Natalie often entices Bianca into trouble, but Bianca is more domineering, often putting Natalie down. Lonely, Natalie makes up an imaginary boyfriend for attention, claiming he has taken her on extravagant dates. This makes Bianca envious initially, but when Natalie's lies are discovered, Bianca takes great pleasure in humiliating her. Natalie gets a job at Bridge Street Cafe but is often arriving late and chatting to Bianca which annoys cafe owner Kathy Beale.
When Tiffany Raymond reappears, Natalie feels sidelined by Bianca as she did in school. Bianca's boyfriend Ricky Butcher also tires of Bianca's selfishness and this inadvertently drives him and Natalie closer together. They console each other and in February 1995, they begin an affair. Ricky is Natalie's first sexual partner and for her it is true love, but Ricky does not take it as seriously. Natalie starts pressuring Ricky to tell Bianca about their relationship and when he does not, Natalie plants some lingerie in his work overalls. Bianca finds it and suspects Ricky is having an affair; she takes Natalie's advice to follow Ricky so she can catch him with the mystery woman. Bianca does this one night and catches them kissing and is incensed. In the aftermath, Ricky dumps Natalie and Bianca threatens her, ordering her to leave Walford. Dejected, Natalie does so, leaving Walford to stay with her sister in Basingstoke.
In 1999, Natalie reappears as a new self-confident business woman, running a dating agency. Barry Evans, unaware of Natalie's history, uses her agency, "Romantic Relations". Despite Natalie's attempts to set Barry up with other female hopefuls, she eventually becomes attracted to him herself and they begin dating. Natalie's reappearance is met unfavourably by Bianca and fights ensue. However, they eventually call a truce and become friends again. Natalie's business does not prosper and closes soon after.
Despite initial problems caused by Natalie's overbearing mother who tries to take over the wedding plans, Natalie and Barry marry on New Years Eve in 1999, in a joint wedding with Ian Beale and Melanie Healy. They live with Barry's father Roy and stepmother Pat and are relatively happy until Natalie becomes pregnant. Preferring to concentrate on her career, and unable to make Barry realise how she feels, Natalie plans an abortion. When Barry comes to the clinic, pledging to support her decision, Natalie changes her mind and does not have the termination. Barry is overjoyed and agrees to give up work and look after the baby so she can work, giving birth to son Jack early in 2002—the birth is traumatic as Jack was born feet first. Motherhood is hard for Natalie; she begins to feel that she has two children, Jack and Barry. When Barry's half brother, Nathan Williams, moves in briefly, he makes Natalie an unsuspecting pawn in his vendetta. Determined to ruin Barry, Nathan tries to seduce Natalie and they kiss briefly but she soon realises that Nathan wants to ruin Barry and banishes him from their lives. Barry forgives Natalie; their marriage remains intact but Natalie grows increasingly unhappy with Barry's immaturity.
Feeling stifled and trapped, she turns to Ricky. They rekindle their affair and decide to leave Albert Square with their sons. On the night of her 26th birthday, while Barry plans a secret party in The Queen Victoria public house, Natalie prepares to leave. Barry discovers what is happening just as Natalie is leaving. Desperate to prove his love, he drags Natalie into the pub and begs her to stay. Natalie breaks Barry's heart by admitting that she does not love him and despite his pleading, refuses to give their marriage another chance. During the chaos, Ricky's sister, Janine Butcher, ruins their plans by telling Natalie about Ricky's one-night stand with Sam Mitchell days before. Confronted by Barry but unable to trust Ricky and racked with guilt, Natalie ends things with Ricky and leaves Walford alone, later divorcing Barry. Janine encourages the divorce and sets a plan in motion to manipulate Barry and steal his money, aided by Paul Trueman, Janine's true boyfriend. This eventually leads to Barry's untimely demise, when Janine pushes him from a cliff and leaves him to die, days after they marry on New Year's Eve 2003 in Scotland. Janine inherits Barry's wealth, leaving Natalie and Jack nothing.
Suspecting foul play, Natalie tries to prove Janine has murdered Barry but is unsuccessful. She refuses to leave with Ricky, who leaves following Janine's confession of what really happened to Barry (but keeps this to himself). While Natalie comes to terms with Barry's death, she gets close to Paul, who is desperate to make amends to Natalie and Jack for his part in Barry's death. Despite his feelings for Natalie, Paul struggles with his guilt and when Natalie gets suspicious about Paul's relationship with Janine, he finally reveals Janine's role in Barry's death and makes a statement to the police. Janine is questioned but released due to lack of evidence. She promptly tells Natalie that Paul conspired with her from the start and gloats about getting away with murder. Devastated, and unable to prove Janine's guilt to the police, Natalie leaves Paul and Albert Square in March 2004. She returns briefly in May to witness Janine's incarceration after she is falsely accused of murdering Laura Beale. Natalie makes peace with Paul, holding a ceremony for Barry by scattering his ashes under a tree planted in his memory. She and Jack leave but it is indicated that Pat stays in touch with Natalie when she goes to stay with her off-screen in 2007, following an accident.