The Duke of Cambridge completed a civilian pilot course in September last year before taking dedicated 999 emergency response training in order to take up the role with the East Anglian Air Ambulance (EAAA).
His first shift, began at Cambridge Airport this morning as a co-pilot alongside medical staff, will be nine-and-a-half hours long.
"It's my first day and I'm feeling the nerves. We're starting off on a wet Cambridge day, but I'm really looking forward to getting started," the 33-year-old told BBC.
He explained: "Obviously at some point there is going to be a lot more pressure and responsibility from the other side of my life, but at the moment I'm juggling the two of them and a young family and I'm enjoying the challenge.
"It's a follow-on from where I was with the military search and rescue with many of the same sorts of skills, so it was a natural progression."
The former Royal Air Force (RAF) helicopter pilot will cover Norfolk, Suffolk, Cambridgeshire and Bedfordshire as part of his duties.
"Nothing ever prepares you that well for what you are going to see," he said.
Prince William had been on paternity leave to spend time with new-born Princess Charlotte at their new family home of Anmer Hall on Queen Elizabeth II's Sandingham estate.
"It has been fantastic and she has been a little joy of heaven.
But at the same time it is more responsibility, looking after two little ones, especially when George is around.
"But it is fantastic having a lovely little family and I am so thrilled. And Catherine (wife Kate) has been doing an amazing job as a mother and I am very proud of her," he added.
Asked whether the couple might have more children, he said: "We've only just had the second one. You never know what is going to happen in the future.
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