The Duchess is a patron for the National Literacy Trust and visited the City Academy in Hackney, London, which was holding the "Words for Work" programme.
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The scheme, which runs in the school through the National Literacy Trust, aims to teach the children business and communication skills.
Nick, who used to run a PR company before becoming Lord Alan Sugar’s right-hand man on the BBC’s The Apprentice, is also an ambassador for the Trust, and led a seminar where he was quizzed by youngsters about a range of issues including how to cope with responsibility.
Nick praised the scheme, saying: "I thought the panel was very good, they worked as a team and asked sensible questions."
Speaking to the Daily Mail, he added: "but I don't know if I got the job!"
Camilla, Duchess of Cornwall
Under the programme, volunteers from the business sector work alongside 13 to 14-year-olds, providing them with the literacy skills needed to get a job as well as helping to raise their confidence.
Camilla, wearing a smart blue skirt suit with a snakeskin clutch bag, joined in the seminar, asking Nick what makes him laugh.
The 70-year-old admitted he laughed "very easily", adding that "humour is the bedrock of a happy life - I have a silly sense of humour."