In-situ analysis of heterogeneous catalysts under reaction condition is indispensable to understand reaction mechanisms and nature of active sites. Ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) is one of the powerful methods to investigate chemical states of catalysts and reaction intermediates adsorbed on the surface. In this review, reaction of carbon dioxide on Cu(997) and Zn-deposited Cu(997) surfaces are discussed as an example of surface chemistry of weakly adsorbed molecules, together with a brief overview of recent progress in AP-XPS methods.