The time–of–flight method was used to study the laser stimulated desorption of atoms and molecules from the surfaces of Cr2O3, ZnO, TiO2, MgO, A12O3 under the influence of radiation of four harmonics of a pulsed neodymium laser. For the oxides studied, the kinetic energy distributions of desorbed oxygen molecules are characterized by the presence of two forms: “fast” with kinetic temperature Tk˜2500–3500 K, and “slow” with Tk˜350–550 K. The first one is typical for desorption excitation in the self-absorption region (hv > Eg), and the second one in the transparent region. “Fast” O2 desorption is accompanied by emission of single oxygen and metal atoms. Two non-thermal mechanisms of desorption are suggested, associated with the nature of the initial state of atoms and molecules on the surface and of the mechanism of the laser excitation of this states. The “slow” molecular oxygen desorption results from the excitation and subsequent neutralization of adsorbed molecular ions. The “fast” O2 emission is the result of recombination of oxygen atoms, after neutralization of the surface lattice ions by photoexcited carriers.