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The couple, who are from Patna in East Ayrshire, were leaving their service at Ayr Town Hall when they bumped into the Prince of Wales who was attending a military parade.
Despite being decked out in a khaki combat uniform, Charles, who is known as the Duke of Rothesay when in Scotland, stopped to offer his congratulations to the smartly-dressed couple and posed for photographs.
"That was absolutely amazing, we were really shocked," said Private Rooney, 28, and his new wife Kirsty, 22. "Who can say they had their wedding photograph taken with the Prince of Wales?
"It's a day we'll remember forever," they added.
Prince Charles had been in Ayr for a parade by the Queen's Own Yeomanry, of which he is the Royal Honorary Colonel.
Earlier on Saturday the future King took a royal salute from from around 150 soldiers at Wallace Tower as they marched through Ayr town centre before attedning an honorary freedom ceremony for the regiment at the Auld Kirk in the town before the civic reception with soldiers and their families.
Hundreds of people lined the stress of Ayr's town centre to attend the parade and catch a glimpse of their royal visitor.