Born in Camborne, Cornwall, England, of British and Irish parents, Zoie Palmer moved with her family to Canada when she was ten years old. She attended Sacred Heart Catholic High School in Newmarket, Ontario; and received a B.F.A. from York University in Toronto, Canada, in 2001. Her sister, Tracey (Palmer) Weiler, was the Progressive Conservative Party of Ontario candidate for the Kitchener-Waterloo electoral district in the 2012 by-election for the Legislative Assembly of Ontario (Ontario Provincial Parliament). Palmer's first experience as an actor was as a teenager in summer stock at The Red Barn Theatre in Sutton West, Ontario, Canada.
Palmer's television work includes made-for-TV movies The Reagans (2003) as Patti Reagan; Out of the Ashes (2003) as Didi Goldstein; Devil's Perch (2005) as Abby. Palmer had a recurring role as rock singer Patsy Sewer in the CTV Canadian teen drama/comedy series Instant Star; she was co-lead in the Global Canadian drama The Guard as Coast Guard rescue specialist Carly Greig (for which she had to conquer her fear of water). Guest appearances include The CW American espionage drama Nikita in the episode "Girl's Best Friend" (2011) as Anya Vimer, a terrorist who tries to sabotage a peace summit; the HBO Canada comedy Call Me Fitz in the episode "Don of the Differently Abled" (2011) as Laura, an unhinged amputee with plans for an escort service for disabled people; the (CTV) Canadian science-fiction crime drama The Listener in the third season finale episode "The Shooting" (2012) as Staff Sgt. McCoy, an investigator for Internal Affairs.