The pop icon spoke out after Loose Women star White told the others how to cook the kangaroo sausages - and fans of the ITV show reckon there's trouble ahead.
Speaking in the Bush Telegraph, George said: “It’s so weird, that [food] bag comes down and Charlene just turns into an entirely different person. It’s amazing, she issues orders and tells everyone what to do. I’m like, ‘Wow’. You know, it’s like, ‘Who are you?’"
He added: “Charlene, she just issues orders. For me as an observer of my own feelings, it’s mind blowing.”
He later said he found White to be “very controlling”.
“She tells you what to do and it really rubs you up the wrong way,” he said.
“I’m struggling with that, but I’ll get over it. It’s fine, she’s very sweet as well so it’s a real contradiction. There’s this controlling side and then there’s this caring side and it confuses me.”
The Culture Club singer told White she was “a beautiful contradiction" and that it was “challenging”.
When she asked why, he replied: "Because I’m such a control freak. It’s my stuff.”
He went on: “Because you are such a matriarch… and you better accept it, don’t even deny it."
George later told White he wasn’t fussed if she told him what to do, but added: “Give me some jobs if you’re going to be the boss.”
“I’m not being the boss!" she replied.
But he snapped straight back: “You are being the boss baby.”
Viewers think it could be the start of some serious tension.
"Charlene vs Boy George!" one tweeted.
Another posted: ""Anyone else see that when Boy George is going to get hungrier as there will be less stars/food, he is going to absolutely FLIP. HIS. LID."
In a nod to the singer's track Karma Chameleon, one joked: "Boy George needs to calma calma calma calm it down."
Watch the next live episode tomorrow at 9pm (Wednesday) on ITV and ITV Hub.
Watch: Vanessa Feltz says Boy George is 'obnoxious' on I'm A Celebrity