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.
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!"
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."
Camilla has had a busy week, as she also visited Chelsea and Westminster Hospital where the couple were due to open the new Chelsea Children’s Hospital.
Camilla, 66, was cradling ten-month-old Maijed Dhaif in her arms when she commented on the baby and her step-grandson Prince George's similarities in age.
"There we are, there we are," said the Duchess as she rocked him gently. "Holding him like this reminds me of George. They're about the same age."
The young prince’s father Prince William recently revealed that the royal tot has learnt how to crawl and his first milk tooth is starting to come through.
George is also "doing well" with his weaning, the proud dad said.