Camilla shone in a floor-length navy blue dress and sparkly black jacket.
Also known as 'The Milles', the ceremony was initiated by the Prince of Wales in 2008 to thank and recognise the incredible role of Britain's Armed Forces.
The couple spoke to the award nominees at a reception before attending the ceremony during which they presented an award for the 'Most Outstanding Airman'.
The 65-year-old Prince then made a short speech.
Upon arrival Their Royal Highnesses were met by representatives of the Chief of the Defence Staff and three Service Chiefs, along with the Mayor of the Royal Borough of Greenwich, Councillor Angela Cornforth.
Charles and Camilla were joined by other VIPs including X Factor judge Amanda Holden, This Morning presenter Holly Willoughby, prime minister David Cameron and his wife Samantha Cameron, I'm A Celeb... contestants and couple Amy Willerton and Joey Essex, popstar Kimberley Walsh and Peter Andre.
Upon launching 'The Millies' 2013 in September, the first in line to the throne said, "It is time once again to launch The Sun’s Military Awards Campaign and begin the search for extraordinary examples of bravery, fortitude, resilience and determination by our Servicemen and women.
"I cannot help but feel that this is the easier part of the task, as there are quite simply so many remarkable examples of soldiers, sailors and airmen and women doing extraordinary things.
"The more difficult task is to try and decide between them just who should receive an award, as they all deserve recognition.
Now in its sixth year, the awards continue to recognise the excellence, sacrifices and contributions made by our servicemen and women, both at home and abroad.
The glittering event celebrates the achievements of the cross-section of the Armed Forces and those who support the Armed Forces on operations at home and abroad. Servicemen and women and civilians have been selected for awards in recognition of outstanding performances and contributions in the military.
Ten awards were due to be presented to groups, individuals and units as recognition of their work within their fields across the Royal Navy, Army and Royal Air Force.
Charles and Camilla attended the ceremonies in 2008, 2010 and 2012. Former RAF helicopter pilot Prince William and Armed Air Forces Apache gunner Harry went along the event in 2009. They were joined by Kate Middleton in 2011.