The versatile Welshman signed a three-year deal with the Scottish club.
James joined Yeovil Town from Cardiff City, he played almost 100 games for the League Two club.
Speaking about the move, James said:
It was definitely the gaffer who swung it for me. He showed how much he wanted me and that was the biggest pull,
As a footballer, you want the manager to be on your side from the start and I feel like he definitely is. I want to repay him for that.
I think he wants me to be a full-back who gets forward and creates chances, though I did play all the way across the back four last season and occasionally in the centre of midfield.
Meanwhile, Hibernian manager, Paul Heckingbottom added:
We’re really pleased to have Tom on board,
He’s a highly-rated young player who can operate in a number of positions, which is obviously advantageous when we want to run with a smaller group.
I know Tom well and we have seen him play many times.
I’m delighted he has bought into what we want to achieve here because he had a lot of other offers.
Tom has good quality, is composed on the ball and has a great attitude to improve. We look forward to working with him.
The 23-year-old defender will become Hibernian fifth signing of the summer.