Prince William had his back to Kate Middleton as she entered the church, as is customary at royal weddings, and Prince Harry could be seen whispering words of encouragement while Middleton made the lengthy four-minute journey down the aisle.
Underneath the public banter, where they regularly poke fun at each other, the pair share a special bond which was strengthened following the death of their mother Diana, Princess of Wales in a Paris auto crash.
When asked by reporters about the reversal in roles during, William, 35, said he was "thrilled and delighted" to have the opportunity to stand by his brother's side on the big day.
"You know, we are uniquely bonded because of what we've been through".
Harry performed best man duties at William and Kate's wedding in 2011.
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The news that Prince William will return the favour is another way Prince Harry and Meghan Markle will be breaking with tradition at their wedding.
According to BBC, the much-awaited wedding will take place at St George's Chapel at Windsor.
Prince Harry who is getting married in May to Meghan Markle has asked that his brother Prince William be his best man.
The event was a service to commemorate and pay tribute to the fallen members of Anzac (Australian and New Zealand Army Corps).
Britain's Prince William is set to miss the FA Cup final while being best man for Prince Harry.
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"It was so sweet and natural and very romantic", Meghan added.
"Punters are rushing to get their bets on as the excitement builds", said Harry Aitkenhead of bookmakers Coral.
Australia's representative Alexander Downer asked William: "Have you thought of the name Alexander for him?" "It's a good name".
The royals know it well and it will give them the privacy to indulge in outdoor pursuits and keep their antics under wraps.
William, who was sitting next to his future sister-in-law, Meghan Markle, was caught on camera as he caught some shut-eye.
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