Change Please coffee will be sold for £2.50 a cup from carts across the capital, with all profits re-invested to train a new cycle of staff.
Each barista will earn the London Living Wage of £9.40 per hour and be housed in temporary accommodation.
Change Please said that after six months it will help employees find long-term work in the food and beverage sectors, with several big companies keen to provide job opportunities.
The carts will launch this week at Covent Garden, Borough and Waterloo, with more central London sites set to be announced soon.
Cemal Ezel, co-founder of Old Spike Roastery, which is partnering the scheme, said the project ‘immediately lifted people out of homelessness’
"We promise one of the best cups of coffee you'll find, but even better, we guarantee that this programme will make a significant contribution to helping alleviate the homeless problem across the country,” said the former commodities trader.
"If we can get a small proportion of coffee drinkers to simply change where they buy their coffee, we really could change the world."
According to The Guardian, the pop-up carts will expand to Bristol, Manchester, Nottingham, Glasgow and Edinburgh over 2016 and eventually provide work for up to 200 new trainees a year. The coffee beans and merchandise are also available to buy online for nationwide delivery.
Peter Bird, Big Issue distribution manager, said: "Selling the Big Issue works well to provide people currently living on the streets with a way to help themselves work towards a better life, but there is a gap between that segment of homelessness and securing a regular job that needed a solution.
"Change Please provides that and will hopefully be the hand up that people need to work their way back in to society."
The Big Issue was founded in 1991 and currently circulates around 100,000 copies a week.
Vendors buy copies for £1.25 and sell for £2.50, keeping all profits they make.