The royal couple visited the renovated Hougoumont farmhouse where allied forces fought off a bloody French advance on June 18, 1815, in one of the most decisive moments in the battle.
Charles, who is heir to the throne, unveiled a statue of two life-size soldiers closing the farm's north gates to commemorate the British, Prussian, Dutch and Belgian soldiers who died.
The event is the opening salvo in a series of commemorations of the Battle of Waterloo, including a ceremony on tomorrow and two days of battle re-enactments on Friday and Saturday.
But the British and Prussian forces led by the Duke of Wellington and Marshal Bluecher held their ground and played a pivotal role in winning the day-long battle at Waterloo, south of the Belgian capital Brussels, that crushed Napoleon's dreams of European conquest.
Wellington said later "the success of the battle turned upon the closing of the gates at Hougoumont."
In the afternoon of the pivotal day, a dozen men from the Coldstream Guards managed to close the north gates of the farm that the French troops had managed to force.
Ten men from the Coldstream Guards wearing the red uniforms of the period symbolically opened the farm gates on Wednesday for Charles and Camilla, while a bugler played the Last Post and a band played the British national anthem "God Save the Queen."
In addition to the British royals, Princess Astrid, sister of King Philippe of Belgium, as well as Prince Pieter-Christian of the Netherlands and the Grand Duke of Luxembourg joined the ceremonies under a warm summer sun.
The current Duke of Wellington, Prince Charles Bonaparte and Prince Bluecher von Statthalter, descendants of the key players in the battle, shook hands before Charles unveiled the memorial.
European royals will attend a solemn memorial service on Thursday at the battlefield.
Nearly 200,000 spectators are also expected to flock to the site for a giant sound-and-light show on Thursday, followed by two days of battle reenactments described as the largest of their kind in the world.
Waterloo is still a sensitive topic in France and organisers are treading carefully to paint the event as a celebration of a modern continent united by the 28-nation European Union after centuries of war.
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