Various deteriorated surfaces of Bi2Sr2CaCu2Oy single crystals are investigated by X‐ray photoelectron spectroscopy (XPS). From the results, it is found that the Ca 2p, 3/2 XPS peak position shifts to the higher‐energy side and its half‐width becomes broader by exposing the air‐cleaved surface of the crystal to an atmosphere of CO2. This indicates that CaCO3 is produced by CO2 gas exposure for 40 min. The valence state of Cu changes from 2+ to 1+ by air, O2, and CO2 gas exposure. Two XPS peaks at about 532 and 531 eV, which are probably related to the impurity oxides and carbonates, respectively, are observed in the XPS spectra of O 1 s core levels.