Members of the Armed Forces, veterans and their families will get shop discounts as part of a new service.
Companies including Vodafone, KFC, Vision Express, Austin Reed and Vue Cinemas have agreed to offer discounts for personnel and their families as part of the new Defence Discount Service (DDS).
The DDS will launch with a website offering online discounts from High Street companies.
It also hopes to offer a privilege card, which will make it easier to access discounts in stores and online.
"We owe a huge debt to the members of the Armed Forces and this new Defence Discount Service is an opportunity for companies to show their gratitude and support," Defence Secretary Philip Hammond said.
"We have had a great response so far but this is just the start and I urge companies large and small, national or local, to come forward over the coming months."
The scheme will be launched in time for the Christmas shopping period.
The Government is also extending two schemes which provide financial support to the children of Armed Forces personnel. Both schemes are part of the Government's commitment to the Armed Forces covenant.
The money paid to schools with children from service families, and the number of children eligible, is being increased.
Currently, schools receive £250 for each child with parents in the Armed Forces, known as Service Pupil Premium. This will increase to £300 in 2013-14. The premium is provided in recognition of the additional pastoral support schools often need to provide for these children.