The historic central Scotland city will be the focal point for UK-wide celebrations of the armed forces on Saturday June 28, 2014.
It will be the second time Scotland has hosted the national event after Edinburgh took on the role in 2011.
The event will take place less than three months before the referendum on Scottish independence on September 18 next year.
Making the announcement, Defence Secretary Philip Hammond said: "I congratulate the city of Stirling on its successful bid to host the UK Armed Forces Day event next year.
"I know that Stirling, with its strong historic military links with the Army and the Royal Air Force, will mount a spectacular celebration of our military and lead the rest of the United Kingdom in honouring our armed forces personnel past and present.
"Our armed forces are an institution that serve and protect all of us as a United Kingdom."
The 2014 event will be the sixth national event since 2009.
This year, Nottingham hosted the national event, with officials estimating 100,000 people attended the city's celebrations. Cardiff and Plymouth have also hosted Armed Forces Day in previous years.
Planning for the Stirling celebration is expected to get under way soon, officials said.
Scottish Secretary Michael Moore said he was delighted the city has been selected.
"Stirling is proud to call itself the Heart of Scotland and I am sure there will be an array of activities planned to make it a superb focal point for the UK-wide celebrations in support of our Armed Forces in communities throughout the country," he said.
"Armed Forces Day is a time to give thanks to those who serve our country in the past and present, and to inspire future generations."
The national event forms part of the broader Armed Forces Day campaign.
Held annually over one week in June, it is a week of celebrations and activities encouraging the public to show their support for the forces.
The MOD received five bids from across the UK to host the 2014 day.
Major General Nick Eeles, the General Officer Commanding Scotland, said: "Scotland has a fine military tradition and Scottish sailors, soldiers and airmen, as well as those from other parts of the United Kingdom and the Commonwealth who are based in Scotland, look forward to taking part in the many celebrations of their service which will be organised around the country.
"Our servicemen and women have a distinguished track record on operations across the world and Armed Forces Day provides an opportunity for the public to say 'thank you' to service personnel and their families for their significant contribution to the nation's security.
"I hope and trust that communities in Scotland and across the United Kingdom will demonstrate their support and appreciation of the Army, Royal Navy and RAF by supporting Armed Forces Day events wherever they are held, but especially at the national event in Stirling."
Stirling's Provost, Mike Robbins, spoke of the city's pride in becoming the focus of next year's events.
He said: "I am particularly pleased because it gives us the chance to pay tribute to all those who are serving in the British forces around the world today.
"It is also a chance to honour the veterans from our area, and across the UK, who have done so much to defend freedom - whether that was in in the Second World War, Korea or in more recent conflicts."
The event will also coincide with the opening of the new Battle of Bannockburn visitor centre.
Holyrood's Veterans Minister, Keith Brown, said: "I am delighted that the UK Armed Forces Day event is coming to Stirling and returning to Scotland so soon after it was held in Edinburgh in 2011.
"That was a magnificent event and this gives a further opportunity for people across Scotland to show how much they support and appreciate the selfless service of our servicemen and women.
"The Scottish Government has demonstrated its full commitment to supporting the Armed Forces community in Scotland. Our policies and initiatives have made a real difference and our approach has been warmly welcomed and acknowledged as being 'ahead of the game' in comparison to the rest of the UK administrations by Veterans Scotland and the military in Scotland."