She was spotted in Oxford Street in London by an agent who inquired if she modeled. She began her modeling career from that point on and continued for nearly a year, before being cast in her first movie role, "Karaoke" (1996) (mini).
Keeley left her husband just after 5 months of marriage. She began dating Matthew Macfadyen (her co-star from the BBC TV series "Spooks" (2002)) shortly after but maintains she never had an affair whilst married to McCallum.