The degradation of Sydney sandstone used to build the heritage St Mary's Cathedral in Sydney, Australia, has been investigated using environmental scanning electron microscopy combined with energy dispersive X-ray spectroscopy. This technique provided the structural details of the cementing clay and an elemental characterization the sandstone. The observed differences in the elemental composition of the unweathered and weathered sandstones were associated with changes to the clay microstructure upon weathering. The results support the substitution theory that Fe3+ replaces Al3+ in the kaolinite clay component upon weathering. An examination of the impurities present prior to a nonstructural iron removal treatment revealed the presence of minerals that may provide a source of the elements responsible for the substitution process.