Army reservists and the partners of military personnel will be given help to find work under plans announced by David Cameron.
Britain's top companies are also being called on to recruit more veterans and bolster the support they offer to workers with links to the forces.
The Prime Minister unveiled the proposals as the UK marks the seventh annual armed forces day, which is held to recognise the sacrifices made by servicemen and women.
Mr Cameron said: "Today, we celebrate our brave servicemen and women who work so hard to keep our country safe.
"It's only right that once they leave the forces we give them the support they need to find a job.
"We also have a responsibility to our reservists and the families of our military personnel for the sacrifices they make.
"So, for the first time we will help them to find work too. Today we are also calling on the private sector to play its part - by signing up to the armed forces covenant to help reservists and veterans into work.
"I want everyone to have the security of a job and the opportunity to get on in life - and we particularly owe support to our veterans, their partners and reservists."
From October, all forces personnel will be eligible for a career transition programme aimed at helping them find a job outside the military. Trial schemes for partners and reservists will also be launched.
Defence Secretary Michael Fallon has written to FTSE 350 companies calling on them to back the armed forces covenant, a pledge that military personnel face no disadvantage as a result of their service.
Lloyds Banking Group, JP Morgan and the AA are among the 39 companies that are signed up.
Chris Simpkins, director general at the Royal British Legion, said: "The Royal British Legion welcomes the government's announcement, and in particular the support for service spouses and early service leavers.
"This was one of the legion's key asks in our manifesto 2015 and we are pleased that it has been acted upon.
"It is important that individuals who are leaving service are properly supported in their transition into civilian life and to compete in the jobs market.
"This announcement will help service leavers and their spouses receive the support they deserve."