A significant feature of the series is that Dove Cameron plays dual roles, one being Liv, an actress who has returned to her home after starring on a popular television series in Hollywood for four years, and the other one being Maddie, Liv's identical twin who remained behind. Another significant feature of the series are documentary-style cutaways where characters speak to the viewers to explain their opinions on various situations in each episode.
Olivia "Liv" Rooney (Dove Cameron) is one of a pair of identical twins of the Rooney family. She is the eldest child of the family and older sister to Joey and Parker. Liv left the family for four years, beginning at the age of 11, to star in a popular television program, "Sing It Loud!", to which she continually refers. During her time on that show, Liv was living with her Aunt Dena. Liv is a sophomore at Ridgewood High. When Liv and Maddie celebrate their sweet sixteen in "Sweet 16-a-Rooney", Karen states that Liv, who was born at 11:56 PM, is six minutes older than Maddie, who was technically born a day later. Liv's siblings affectionately call her "Hollywood". At the end of the first season, Liv begins production on "Space Werewolves", a film adaptation of a fictional graphic novel series of the same name. Liv stars as Tristan Lycanth in the film adaptation after being able to fully master all the traits of the wolf with the help of writer Emmy "Fangs" Wulfert. Although the protagonist of the story was originally a boy in the graphic novels, Liv was picked for the role because of her acting career on "Sing It Loud!" and the role of Tristan was changed from a boy to a girl.
In "Skate-a-Rooney", it is referenced that between seasons of "Sing It Loud!", Liv filmed a movie called "The Skateboard Bandit". In "Brain-a-Rooney", Liv shows that she is smarter than people think she is by helping Joey and Artie win the Brain Olympics. It is shown that Liv shares the personality quirks of her mother, Karen, as seen in "Shoe-a-Rooney", when the pair reveals their affinity for shoes. In "Voltage-a-Rooney", Liv stars in a TV series adaption of the comic series "Voltage" that was mentioned in "Continued-a-Rooney". She portrays a cheerleader named Tess who was struck by lightning and becomes the superhero SkyVolt. In "Californi-a-Rooney", Liv and Maddie have a falling out at the time when Maddie goes to live with Aunt Dena after being accepted to the same college that Willow is at. After the two of them reconcile, Liv is persuaded by Maddie to stay with her. In "Linda and Heather-a-Rooney", the effects of Liv leaving Voltage to be with Maddie caused her to have a hard time finding another role. She does get a guest role on "Linda and Heather" which she nearly causes to stop production until she and Parker come up with a plan to keep it from ending. By the end of the episode, Liv is told that they want her to reprise her character for the sequel to "Sing It Loud!" called "Sing It Louder!!"

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