On Her Majesty's Service, which saw Barlow travel around the Commonwealth to record his number one single 'Sing', will be available to purchase on June 25.
Over 7 million people tuned in to watch the documentary on its first airing on BBC One earlier this month, leading to the album and single leaping to the top of the charts.
The DVD will include never-before-seen footage and deleted scenes from Barlow's journey.
Barlow said of the programme: "We went on a journey with this record, meeting and recording with some beautifully talented singers and musicians.
"I can't believe we've managed to get the amount of people we got featured on this song, from all corners of The Commonwealth, but we did!
"I'm very proud of the result and hope people enjoy listening to it as much as we enjoyed making it."
Executive producer Ben Winston added: "This has been a wonderful film to be part of. The response to it has been overwhelming. I don't think when Gary and I first talked about this project we could have ever imagined the impact it would have had.
"A number one single and album, the live performance at Buckingham Palace, and the reaction to the amazing characters we found all over the world.
"Working with Gary has been fantastic, he is such a talent, but it's his warmth and humour that really come out in this film. I feel like this is the film where he truly shows who he is."
Gary Barlow was awarded an OBE in The Queen's Birthday Honours list following his involvement with the Diamond Jubilee celebrations.