Munro learned to fly in Tiger Moths at the RNZAF's Flying Training School at Bell Block near New Plymouth, and on graduation chose to fly bombers so was posted to Canada for initial bomber training. He trained on twin-engine aircraft in Saskatchewan at RCAF Station Saskatoon, the present-day John G. Diefenbaker International Airport. He moved to England in October 1941 for further training, and joined 97 Squadron atWoodhall Spa in Lincolnshire. There, he flew Avro Manchesters and then Avro Lancasters in 1942/43 and while there his DFC was gazetted, on 11 June 1943.

He was one of hundreds of aircrew volunteering to be part of the secretive 617 Dambusters Squadron being formed at RAF Scampton, and joined it four days after it was formed, on 25 March 1943. The squadron was created to attack the dams of the Ruhr in an effort to wreck the industrial capacity of Germany. Of the 19 Lancasters that flew on that full-moon night, only 11 returned. Munro, as pilot of W-Willie, was scheduled to bomb the Sorpe dam. Over the Netherlands, his aircraft was damaged by flak which knocked out all communications, so it turned back to land in Lincolnshire, still carrying its mine. His DSO was awarded while he was with 617, on 28 March 1943.

Munro was promoted to Squadron Leader on 14 February 1944 and was posted to command 1690 BDTF Squadron (Bomber Defence Training Flight) on 13 July 1944. His logbook shows that when departing Scampton to bomb Bremen with four 500 lb general purpose bombs, his aircraft crashed and burned shortly after takeoff, but the crew escaped.

Munro took part in Operation Taxable in conjunction with the D Day landings in Normandy in which the Lancasters flew precise, elongated circuits dropping Window(aluminium strips), to convince German radar installations that a huge flotilla of ships was approaching Cap d'Antifer. The ruse was successful and the last of the 617 squadron Window droppers witnessed German shore batteries firing on the "Ghost" convoy.

Munro described the operation in his logbook as:

"The creation of a tactical surprise to support the landing of troops on the opening of the second front. The most hazardous, difficult and most dangerous operation ever undertaken in the history of air warfare. Involved flying within at least nine miles of the enemy coast without fighter cover, and in conditions of bright moonlight and at a height of not more than 3000 ft (three thousand) at which the aircraft was open to attack by the deadliest of all weapons – light flak."

Munro's co-pilot on this operation was Wing Commander Leonard Cheshire, the squadron's commanding officer who later was awarded the Victoria Cross.

He was released from the Royal Air Force on 5 February 1946, a veteran of 58 missions, and he retired from flying. In an 2006 interview, Munro said of his war experiences that he "...would be the first to admit that I was pretty lucky. Most blokes who survived even a couple of operational tours would say that luck was on their side

Following his career in the military, Munro returned to New Zealand where he worked as a property valuer for a time and then on farms in the King Country before establishing his own farm near Te Kuiti. For some time he was involved in local politics as a councillor, and served as Mayor of Waitomo District Council from 1978 to 1995. On retirement, he moved to live in Tauranga.

Munro attended the 60th Anniversary commemoration of the Dambusters raid, along with the Queen and the Duke of Edinburgh in May 2003 at RAF Lossiemouth.He was also present, along with Richard Todd, the actor who played Wing Commander Guy Gibson in the 1955 The Dam Busters film, for the 65th anniversary commemoration held at Derwent Reservoir (Derbyshire) on 16 May 2008. As the last living pilot of the strike team, Munro joined the production crew in Masterton as technical adviser on a remake of the film.

Munro's signature was appended to two sets of souvenir first day covers issued in Britain to commemorate the 65th anniversary of Operation Chastise. One, postmarked "Scampton, 17th May 2008", was signed by the six surviving crew members who flew on the raid, and the other, postmarked '’617 squadron, Scampton'’ was signed by Munro alone.

In 2009, Munro took part in filming for the documentary Into the Wind, directed by Steven Hatton. The film, a feature length documentary about the veterans of Bomber Command, was released on 30 November 2011.

He has a street named in Te Kuiti, Les Munro Place.

In 2014, his portrait was painted by Richard Stone, an artist famous for his paintings of royals, including Queen Elizabeth II and the Queen Mother. On 14 April 2015, he was one of eight New Zealand servicemen who were awarded the Legion of Honour by the French Ambassador to New Zealand.

Munro died on 4 August 2015 in hospital at Tauranga, New Zealand, at the age of 96, after being ill with heart problems

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