Failure of steam-side oxide scales on boiler tubes can seriously influence the safety of coal-fired power plants. Uniaxial tensile tests employing acoustic emission (AE) monitoring were performed, in this work, to investigate the failure behavior of steam-side oxide scales on T22 alloy boiler superheater tubes. The characteristic frequency spectra of the captured AE signals were obtained by performing fast Fourier transform. Three distinct peak frequency bands, 100-170, 175-250, and 280-390 kHz, encountered in different testing stages were identified in the frequency spectra, which were confirmed to, respectively, correspond to substrate plastic deformation, oxide vertical cracking, and oxide spalling with the aid of scanning electronic microscopy observations, and can thus be used for distinguishing different oxide failure mechanisms. Finally, the critical cracking strain of the oxide scale and the interfacial shear strength of the oxide/substrate interface were estimated, which are the critical parameters urgently desired for modeling the failure behavior of steam-side oxide scales on boiler tubes of coal-fired power plants.