The Golden Ratio has been used in architecture since the Classical Era of Greece and Egypt. Both civilizations made full use of the Golden Ratio, developing and improving it. During the Golden Age of Pericles, the Greeks made their largest contribution to the Golden Ratio. At this time, Greece was graced with the minds of Pythagoras and others.
Below is a diagram of one of the Great Pyramids of Giza. Most Egyptian pyramids were more or less based on the Golden Ratio, at least until the New Kingdom, when pyramid building entered a steep decline. The actual pyramid diagrammed below is 481 feet wide by 756 feet long, giving it a ratio of width to lenght of 1 to 1.571.
The Greeks, meanwhile, used the Golden Rectangle to design the Pantheon, a temple in the Acropolis, Athens' foremost religious center.