The former health secretary, 44, and his 23-year-old campmate Owen Warner, known as Romeo Nightingale in Hollyoaks, were chosen for Friday’s trial in a public vote.
They played a jungle-themed version of Who Wants To Be A Millionaire? entitled Who Wants To Look Silly On Air?
Learning he would be taking part, Hancock laughed and said: “That was the most predictable outcome. It’s called looking silly on air, it will be me then."
All the campmates watched on as co-hosts Ant McPartlin and Declan Donnelly explained they would need to secure 11 stars to feed the entire camp.
The presenting duo asked them six multiple choice questions with 60 seconds to answer each, and the help of various lifelines.
Hancock and Warner were drenched in brown sauce before using Ask The Hosts to make McPartlin correctly answer who plays Sirius Black in the Harry Potter movies - Gary Oldman.
They failed to guess which Australian city the Hemsworth brothers were born in, while another question was halted after the campmates tried to cough when the correct answer was read out.
Hancock and Warner then called Sue Cleaver for help using her as their Phone A Friend for a question that involved the year Coronation Street started.
The soap star was drenched while she took the call, with Warner shouting: "Leave Sue alone!"
The pair continued to be pelted with feathers, custard and other messy substances before the challenge ended and they were told they had only secured five out of the 11 stars.
A downcast Warner said: "I’m not happy man, I’m covered in all sorts and we’ve only got five stars. He (Matt) was doing well until you got me on his team."
The episode also saw Boy George recall coming out to his family as a young man.
Speaking to presenter Charlene White, he remembered his early fashion choices, saying: "My mum would say (to my dad): ‘Look at what’s he’s wearing.’
"And my dad used to get his paper (and drop it down to look) and go: ‘If he wants to get beat up let him go out.’ And that was it you know?"
Asked by White whether his sexuality was a surprise to those close to him, the singer replied: "No. My dad used to do this thing in the car, he’d turn down the music when he was going to make an announcement.
"My brothers were all going to work, he was like, radio down, he goes: ‘I need to tell you about your brother.’ They said: ‘We know, turn the music up."’
I’m A Celebrity... Get Me Out Of Here! continues on ITV at 9pm.