James, who was voted out of the show on Friday night, said that the Stoke nightclub promoter was playing games in the house to ensure that he had a chance of winning the £100,000 prize.
[Photo gallery - Day 12 in Big Brother]
Copyright: Channel 5
"Luke is playing the nice guy so he doesn't get nominated and it's fake. He'll do whatever it takes to win," James told the Daily Star.
"He's got into a relationship with Ashleigh Hughes but it's not real. Quite a few housemates think it's fake.
"He could hurt her feelings by doing it because she likes him. I think they will end up having big arguments."
The bailiff and bouncer confessed that his main regret in the house was drinking, because his mum had warned him about his argumentative temper after he's had alcohol.
Big Brother continues every night on Channel 5.