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Social media was awash with pictures of members of the public meeting the duke while he carried out his charitable duties.
One person who had his photo with Prince William was cabbie Neil Kramer.
He said he had been charging up his taxi on Rochester Row in Westminster when he was approached by a vendor who introduced himself as ‘William’ and asked whether he would like to buy a copy.
Mr Kramer told The Standard: “When I realised who it was, I was a bit shocked but of course said yes.
“He then introduced the other gentlemen with him and we had a lovely chat for 15 mins about the charity and it’s work.
“I was asked if I was a regular reader and pointed out there is always an opportunity to buy the magazine when on a rank or charging up.
“All of sudden I was made aware of a group of people who had also noticed who I was talking too.”
Mr Kramer described Prince William as “engaging, polite and never forgot my name”.
He added: “As they both left, I wished them luck and then pinched myself. What a lovely surprise on a random Wednesday and after the Jubilee celebrations over the weekend.”
Retired Met Police chief superintendent Matthew Gardner also shared photos of William on his Linkedin account after his brother-in-law’s saw the future king’s “covert” volunteering efforts.
He said: “My bother in law was in London today and saw a celebrity, so he took a photo at a distance. The celebrity saw the ‘covert surveillance’ effort and crossed the road to investigate further.
“What an honour to have a private moment with our future King who was humble and working quietly in the background, helping the most needy.
“These ‘silent gestures’ often go unrecognised. The finale to this unique occasion was when Prince William asked my brother in law If he wanted to buy the ‘Big Issue’, to which he replied “I have no change”.
“At this point William produced a mobile card machine… You cannot teach that! Priceless, or should I say ‘Princely’.”
The original post has received more than 11,000 likes, with many praising the prince for his charitable work.
Among the comments, one person said: “Wow! An outstanding gesture”.
Another wrote: “True integrity......doing the right thing when nobody is watching”.
Other people have also shared pictures of their chance meeting with the prince while he was carrying out his charitable efforts.
A member of the public who met him said: “Bumped into to the Duke of Cambridge today while exploring London. A true gentleman, a noble cause, and one exceptionally memorable first trip to England.”
The Duke and Duchess of Cambridge Family Album - In pictures
However, Kensington Palace has remained tight-lipped over the pictures.
A spokesperson for Kensington Palace told the Standard: “It is not something we are commenting on.”