Surface analysis of bismuth‐based high‐Tcsuperconductors, like Bi2Sr2CaCu2O8+&dgr;(Bi‐2212) and Bi2Sr2Ca2Cu3O10+&dgr;(Bi‐2223) has been carried out by secondary ion mass spectrometry and x‐ray photoelectron spectroscopy techniques. The results have been compared with that of similar measurements on Bi2O3, CuO, and CaCO3samples so as to have detailed information about the surface binding energy as well as the chemical nature of the various individual components that exist inside these high‐Tccompounds. ©1995 American Institute of Physics.