Enhanced oxidation of ZnS and ZnSe semiconductor surfaces has been observedinsituduring electron irradiation in a high‐resolution electron microscope. The phase present at the surface region has been identified as ZnO by optical diffractogram and selected area electron diffraction techniques. For ZnS oxidation, both hexagonal ZnO having a random orientation and cubic ZnO in perfect epitaxial relationship with the bulk ZnS were observed. Enhanced oxidation of ZnSe to ZnO has also been observed under electron beam irradiation. However, only the hexagonal form was observed. The oxidation rates for both ZnS and ZnSe depended on electron flux but was independent of orientation. A model in which the oxidation process is limited by diffusion through the oxide film is proposed. By electron irradiation the diffusion rate is enhanced presumably by a nonthermal process.