The 28-year-old – who enjoyed an eight-week run on hit BBC show The Apprentice last year before being told “you’re fired” by Lord Alan Sugar – was met by cheers as he walked into the famous abode on Thursdsay night.
Before heading into the house, James said: “I’m confident, cute and on the ball.
“I’m going to go in there and be myself – it’ll be fun.
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“I’ve got serious OCD so I’ll be hard to live with.”
Stars from both the UK and USA are taking part in this year’s fly-on-the-wall contest.
Other contestants include Loose Woman Sherrie Hewson, Atomic Kitten star Natasha Hamilton, presenter Gail Porter, Put Your Hands Up singer Fatman Scoop, reality TV personality Farrah Abraham and porn star Jenna Jameson.
James, of Chatsworth Road, will be hoping for some success in the hit Channel 5 TV series after a tough few months personally.
In May, he and his dad Jason Hill admitted “serious” health and safety breaches which put the lives of staff and customers at Havana Whites in Corporation Street, Chesterfield, at risk.
He was fined more than £6,000 while his dad – who was described as “potless” and depressed during a hearing at Chesterfield magistrates’ court – was ordered to pay out more than £10,000.
Meanwhile, one of James’s companies, Aspire Specialist Care Ltd, is in the process of being liquidated.
He resigned as a director of the firm – which ran the disgraced St Jospeh’s Specialist Care Home – last September ahead of his appearance on The Apprentice.
James said that since his resignation from he company he has had no involvement in the running of the home in Newbold Road, Chesterfield.
Earlier this month, the Care Quality Commission published a shock report on standards at the home following an inspection in May which resulted in five residents with learning difficulties being moved to alternative accommodation.
The home is now shut.
A 49-year-old Matlock man who was arrested on suspicion of assault following the home’s closure remains on police bail pending further enquiries.
It is believed that Celebrity Big Brother show fees start from £20,000 for just a matter of weeks inside the house and can range up to £400,000.