The new Co-operative store in East Craigs will be almost entirely staffed by people who have been off work due to a variety of physical and mental conditions.
The agreement was struck between Co-op bosses and the government-funded Ingeus organisation, which specialises in pro-actively getting people back to work.
It is one of the biggest deals of its kind in the Lothians, with those behind it saying it will improve the wellbeing of the new employees as well as getting them off benefits.
Ingeus' employer and partnerships co-ordinator, Craig Purves, said both parties stood to benefit from the scheme.
He said: "We've got a massive range of individuals we work with, from former managing directors to people who have never been in the workplace before.
"They could have been in receipt of a health benefit for a number of reasons, both physical and psychological.
"It makes sense for people who could work to try and get back, because there is plenty of evidence that it is actually good for your health to be working.
"There really is a great deal of excitement, and I suppose some relief too, among those who will be starting work here.
"It is a great opportunity for them, and the fact it is a well-known company helps as well."
The ages of those starting work at the Co-op at Bughtlin Market, which is due to open on December 9, range from 19 to late 50s.
The majority will be full-time customer assistants, in addition to two supervisors.
Those working at the shop will still retain links with Ingeus, which will offer in-work support and advice to those who need it.
The scale of the agreement has also prompted calls for more businesses to explore linking up with such schemes.
Organisers said even smaller companies could find they are unearthing staff who - though lacking recent experience - have a wealth of knowledge and qualifications.
Emma Johnstone, Co-op's regional human resources manager, said: "This is what the Co-op is about, which is being right at the centre of the community.
"We are not an organisation that discriminates. Some businesses may be reluctant to take on so many people who have been out of work long-term, but as far as we are concerned they have as much chance of succeeding as anyone else.
"They didn't choose to be on benefits, and at a meeting we had they all seemed really keen to get started, which isn't always an experience you have when hiring new staff."
'I feel like I'm a proper person again'
WHEN Alan Farrell lost four close relatives in a short space of time, he sank into a depression deep enough to stop him working.
The Peffermill man had previously held senior jobs in pubs and worked for a spell for the Royal Mail.
But when his depression worsened, prompted largely by the death of his mother, he was signed off and remained on the sidelines for 18 months.
"I had no plan, no direction and no idea what I was doing with my life," said the 38-year-old, who is one of 21 who will start work as a supervisor at the new Co-op in East Craigs.
"Thankfully I became involved with Ingeus and things began to change. It was clear they had only my interests at heart.
"They helped me when I needed help, pushed and prodded me when I needed it too, which you need in that situation.
"Now I'm really looking forward to getting back to work, to become a proper part of society again.
"I feel like I'm a proper person once more."