Goldsmith, who is Carole Middleton’s younger brother, wasted no time in exploiting his royal links after his energetic arrival on the ITV1 show on Monday evening.
However, he admitted it was “difficult to get hold of Kate at the best of times”.
As the father of one discussed the royal family with television personalities Louis Walsh and Sharon Osborne, he was asked if it was difficult being related to famous people.
“I didn’t vote for it, it happened to me, and then suddenly there’s a spotlight on you,” Goldsmith replied.
“They call me the buncle. Have you heard of a buncle? Bad uncle, apparently every family has them.
“It’s difficult to get hold of Kate at the best of times, and she’s got children and I love the fact that she’s putting family first.”
The businessman said he believed the prince and princess were both “the saviour of the toyal family”, before Walsh said: “I have to ask you, have you met Meghan Markle?”
His response will be broadcast on Tuesday night’s show.
He told The Sun the princess was “beautiful on the inside” and a doting mother, describing the monarchy as “family-centric”.
“That’s why I got so upset with Harry and Meghan because you don’t put a stick into that spoke and reinvent history,” he said.
“I got pretty miffed when they had a pop at my beautiful niece who couldn’t say anything for herself.”
Meanwhile, as he entered the house, he described the princess as “simply perfect”.
Asked if she would be watching the show, he said: “If she is, it will be behind the sofa I guess … It will be a nice one in a nice house, I can guarantee that.”
Goldsmith revealed: “The first time I met William, Catherine was cooking and William said ‘Hi, do you want a cup of tea’? Very normal.”
The tattooed father of one, known to his royal niece as Uncle G, has often been described as the “black sheep” of the family.
In 2009, he was filmed by undercover reporters at his Ibiza villa, La Maison de Bang Bang, apparently cutting up cocaine on the kitchen worktop; and in 2017, he narrowly avoided jail after being convicted of attacking his wife during a drunken street row.
He has admitted he does not “take instruction or being controlled very well”.
Goldsmith was joined on the show by an array of celebrities including television personalities Sharon Osbourne and Fern Britton, music manager and broadcaster Louis Walsh, and chef Levi Roots.
The series will be on television for almost three weeks.
A Kensington Palace spokesman refused to be drawn into a conversation about Celebrity Big Brother, which first aired on Channel 4 in 2000.