The Lifehouse squad from the Salvation Army's Booth House in Brixton earned their place in the fixture on Tuesday after winning a tournament involving other homeless centres and supported housing units, last autumn.
The five-a-side clash at Whittington Park Football Pitch in London saw them take on a team of both Conservative and Labour members of Parliament.
Jamel Paxton, 25, resident at Booth House, said: "The match was great. It was nice to socialise with people, understand people from a different perspective, and different walks of life.
"I am looking forward to having a chat with the MPs, and to understand their political views. It is great to have been able to raise awareness but also to understand that the MPs are people too."
The Salvation Army's Deputy Territorial Director of Homelessness Services, Major Howard Russell, added: "We hope this helps [the residents] realise they can make a positive difference in their lives.
"We believe experiences like this help promote a healthy lifestyle with our residents or former residents as well as developing life skills."
Clive Betts MP (Lab), for Sheffield South East, said: "Recognising many of the [Booth House] team have been homeless and to just come and have a chance to have a great game of football and enjoy their company in a competitive and good game was fantastic."
Mark Spencer MP (Con), for Sherwood, added: "Wherever you are, you can find yourself in challenging circumstances, and I think it's good for MPs to come and engage with people who've found themselves in those difficulties and listen to those stories."