The Preah Vihear monument in Cambodia, located close to the border with Thailand, was one of the Khmer temples registered on the UNESCO World Heritage List as a Cultural Property in 2008. It consists of masonry buildings constructed of siliceous sandstone blocks. In this study, the construction sequence of its buildings was inferred from the chemical composition, magnetic susceptibility, and size of the sandstone blocks, along with pediment end style, and the presence or absence of reliefs on the tympana of adjacent buildings. Five construction stages were identified. We revealed that the Western Annex Hall (N2) is the oldest edifice in the Preah Vihear monument. We also reconfirmed that the Preah Vihear monument was constructed over a range of years, spanning the Bakheng style period to the Angkor Wat style period (the end of the 9th century to the end of 12th century). It was clarified that during the construction of Preah Vihear, the style of pediment ends changed from pediments ending in scrolls made from one block, to pediments ending in scrolls made from two blocks, and finally to pediments ending in five-headed nagas. Over the same time span, the size of the sandstone blocks used in construction increased markedly.