Vicki Donovan is Matt Donovan's older sister. Vicki was a troubled girl and was addicted to drugs. She was being taken care of by Matt, for their mother has left them. In the beginning of the series she was dating Tyler Lockwood, however Jeremy Gilbert also had feelings for her. Vicki and Jeremy hooked up a few times but Vicki didn't want people to find out, since Vicki was older than Jeremy, but Jeremy didn't care. Later on, Vicki, acknowledging that she had feelings for Jeremy too, later breaks up with Tyler and starts a relationship with Jeremy. She was later turned into a vampire by Damon Salvatore.

As a vampire she was not able to control her lust for blood and when she starts attacking Jeremy, Stefan Salvatore kills her with a stake through her heart. Stefan and Damon make it seem as if Vicki had left town. Later in season one, her body was found by Caroline Forbes, devastating Matt and Jeremy. After Jeremy gets shot and Bonnie Bennett brings him back to life, he was able to see and communicate with Vicki, who asks for his help. When Jeremy tells Matt about seeing Vicki, he drowns himself only to be saved by Bonnie with CPR. Since then, Matt was also able to see Vicki. She tells him that with his help, the original witch can make sure she can come back whenever she wants without needing Matt to think about her. However, Matt later finds out that the original witch ordered Vicki to kill Elena in return, so with the help of Bonnie, he makes her return to "The Other Side" and shuts her out of his thoughts.

She later returns in the Season 5 episode 500 Years of Solitude to ask Jeremy and Bonnie to tell Matt to stop sleeping with Rebekah. She later reappears on the other side in the episode Resident Evil when Liz Forbes kills Matt where she is pulled away from the other side in a similar way to Katherine in Gone Girl.