But the former Manchester United star soon convinced the experienced Dragon that she had nothing to worry about.
Neville will make his first appearance as a guest panellist, alongside American fashion tycoon Emma Grede, when the show returns to screens on Thursday, January 4.
As co-owner of League Two club Salford City and Manchester's Hotel Football, Neville knows what it takes to succeed in the world of business.
He also owns the company, Relentless, which was behind a £120million redevelopment of mixed-space offices in Manchester.
Meanwhile, Grede is the founder of shapewear brand SKIMS and the co-founder of Good American, a clothing brand launched in partnership with Khloé Kardashian.
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Speaking to Virgin Radio, Meaden explained that the thought of introducing guest panellists to the show had initially caused some concern.
She told us: "When things change like that, and Dragon's Den has been that format for a long time, everybody was like 'I wonder how this will all work?'"
But she admitted that after working with the pair herself, all her doubts were soon cast aside.
She said: "Well, I gotta tell you, it works! Emma Grede and Gary Neville are absolutely brilliant.
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"I think the worry is, when you're getting a new Dragon in, that it's going to take them a day to get the hang of it.
"If they're only there for a day, then that's a problem but they still sat in those chairs and it was like they've been there forever."
She added: "Gary sat next to me… he's a businessman, he's smart. Emma's a businesswoman, she's smart and she instinctively knows the right questions to ask and instinctively understands."
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Neville and Grede will sit alongside regular Dragons Meaden, Peter Jones, Touker Suleyman and Steven Bartlett as hopeful contestants bid to receive financial backing for business proposals.
And if there was any doubt as to just how real the stakes were, Meaden insisted everything seen on the show is completely 'real'.
She said: "It's our money. We're genuinely asking those questions. We don't wear earpieces, we don't get any instruction.
"There's no direction. We just sit there and we do our thing."