2005–2008: Hollyoaks
McKee auditioned for the role of Hollyoaks character Louise Summers in 2004 as part of Hollyoaks: On the Pull, a nationwide search to find a new actor. After being chosen from over 35,000 applicants, McKee began portraying Louise, who was introduced by series producer David Hanson in 2005.
In 2008, McKee hinted at a possible exit for her character despite refusing claims that she wanted to leave. She told Look magazine: "I'm not going to be there forever. I don't mind the long hours but I'll have been doing that for four years in October when my contract ends." After her contract ended in October 2008, McKee decided to leave the show to focus on other projects, mainly theatre. Several months after her final on-screen appearance, tabloid newspapers began to speculate that McKee would reprise the role to coincide with the exit of Jamie Lomas's character, Warren. McKee had previously told Digital Spy: "Well, Louise might not be dead! That's the exciting twist in the future... On screen, you'll feel like she's dead but depending on me and whether I want to come back for an episode in March — I might be back. I filmed an extra scene showing that I'm still alive. There are flashbacks which show me being killed, but then there's a flashback which viewers won't see for a while, that will be used if I choose to come back for the episode. I kind of want to come back and finish off Louise's storyline, but at the moment, I might be doing something else. It would be really good, though — I'd be going back to kill a few people off."
Following McKee's decision to leave the show, she said: "I have enjoyed my time at Hollyoaks immensely and I'm going to really miss everyone at Lime Pictures. I have learned so much and will take away with me many happy memories — not just from everyone I have worked with but from Liverpool as a city too, which has become my second home. I know I will shed a few tears on the day I leave but I am so excited about what the future holds." Hollyoaks series producer Bryan Kirkwood commented on her departure, stating: "As well as being the nation's sexiest soap star for two years running, Roxanne has worked incredibly hard to prove herself as a talented actress. She has been at the centre of one of our biggest storylines for the past two years and her exit scenes will be a fitting climax. Roxanne is a real star in the making and I'm sure this won't be the last that we hear of her." McKee says she was asked to return to the role about a year after leaving the show, but she declined.
McKee won the award 'Sexiest Female' at The British Soap Awards in 2007 and 2008, an award she had been nominated for in 2006 and 2009. McKee was also won 'Sexiest Female' at the Inside Soap Awards in 2007 and 2008. In 2008 she was also nominated for 'Best Actress'. Virgin Media profiled some of Hollyoaks' "hottest females" in their opinion, of Louise they stated: "It's no surprise that sultry Roxanne McKee was voted sexiest soap star for two years running at the British Soap Awards. She's so foxy that even on-screen fiancé Warren was sad he had to finish her off."
