The photo captures a powerful moment where two former drug addicts are reading the New Testament together.
It was taken by Paul Triller while in Romania and impressed the judging panel with its immediate impact, fantastic use of light and real intensity.
Triller was handed a camera-shaped trophy by emerging artist Craig Dyson during the award ceremony, which was also attended by judging panel members, renowned photojournalist Don McCullin and Baroness Warsi.
The annual Faith Through a Lens competition was created by national church insurer Congregational & General in partnership with the Inter Faith Network to raise the profile of faith in the community.
Triller received the award in the Moments of Faith category. The other two awards were for A Year of Service, won by Rob Boler, and Community Spirit Against the Odds, won by Sara Phipps.
Congregational's Marketing Manager, Margaret Slater, said: "This year's competition has seen a fantastic number of entries, underlining how faith is outplayed in many different scenarios in society. Our winning image, 'Brothers in Arms', captures this in a wonderful way and we're delighted to announce it as winner.
"Congregational is committed to supporting and nurturing community groups and faith-based organisations across the UK.
"We're thrilled that each of our three winners are now able to choose such an organisation to benefit from £1,000 of audio-visual and photographic equipment."
Communities Secretary Eric Pickles said: "They say a picture is worth a thousand words and I was delighted to see A Year of Service really come alive in some terrific photos that perfectly captured the strength of our faith communities and the commitment they make to their neighbourhoods.
"This has been a memorable year of social action so thank you to all the budding photographers who entered and congratulations to the winners."
Faith Minister Baroness Warsi said: "These photos really illustrate what can be achieved when communities join together, so it was fantastic to see all of the photographs that were submitted for the competition.
"Thank you to all those who took part, it is great to have a permanent record of A Year of Service events - here's to another successful year of faith volunteering and social action."