The absorption of CO2laser radiation inp‐type GaAs is dominated by direct free‐hole transitions between states in the heavy‐ and light‐hole bands. For laser intensities on the order of 10 MW/cm2, we report that the absorption associated with these transitions in moderately Zn‐doped GaAs (∼1017cm−3) begins to saturate in a manner predicted by an inhomogeneously broadened two‐level model. At higher laser intensities surface melting occurs initially at localized sites in moderately doped material and more uniformly in heavily Zn‐doped samples (≳1018cm−3). As the energy density of the CO2laser radiation is progressively increased further, the surface topography of the samples shows signs of ripple patterns, high local stress, vaporization of material, and exfoliation of solid GaAs fragments. Electron‐induced x‐ray emission data taken on the laser‐melted samples show that there is a loss of As, compared to Ga, from the surface during the high‐temperature cycling. By irradiating the samples in air, argon, and vacuum, we find that the vaporization rates are directly influenced by the ambient environment, particularly by the interaction of oxygen with the molten GaAs. Secondary ion mass spectrometry measurements are used to study the diffusion of oxygen from the native oxide and the incorporation of oxygen in the near‐surface region of the GaAs samples that have been melted by a CO2laser pulse. We find that oxygen incorporation does occur, and that the amount and depth of the oxygen incorporation depends on the laser energy density, number of laser shots, and ambient environment. For samples that are irradiated in argon or vacuum, we find that removal of the native oxide can be accomplished with CO2laser pulses. Similar measurements are performed on Si‐implanted GaAs, and results are reported for the redistribution of the implanted silicon atoms, the deviations from stoichiometry, and the incorporation of oxygen in the resolidified layer.