X‐ray photoelectron spectroscopy has been used to study the surface composition and chemistry of two perovskites: SrTiO3and Pb(Zr,Ti)O3(commonly known as PZT). It is seen that ion bombardment, which is a common surface modification technique, can cause substantial changes in these oxides. The PZT surface undergoes surface depletion of lead along with chemical reduction of the Pb2+ion to its metallic state. The Zr/(Ti+Zr) ratio also changes with sputtering, but the total oxygen to cation ratio is unchanged. On the other hand, the surface stoichiometry of SrTiO3is almost unaffected by ion bombardment. In all the perovskites, irrespective of whether the composition changes or not, a substantial amount of surface Ti is reduced to a lower valency state on sputtering. Most of this component is restored back to the original Ti4+state when Ni is evaporated on these surfaces, indicating that the reduced state is associated with a damaged outermost surface that can be repaired with an adsorbate. The implication of these results to the bonding properties of these materials have been discussed.