The primary products of desorption from Al₂O₃ surface excited by laser pulses (pulse duration τ ∼~ 15 ns; wavelength λ = 354 nm, radiant power density P/S < 10⁸ W/cm²) in the V-center absorption band were studied by the time-of-flight (TOF) spectroscopy. The TOF spectra show evidence of the desorption of one "cold" (T₁ = 300 K) and two "hot" (T₂ = 1000 K, T₃ = 4300 K) groups of oxygen molecules with the Maxwell velocity distributions, as well as of the hot Al and O atoms with nonequilibrium energy distributions (E₁ = 0.37 eV, E₂ = 0.38 eV). A model describing the oxygen desorption as initiated by the electron transitions is suggested, in which escape of the cold O₂ molecules from the surface is related to discharge of the O^- ₂ anions adsorbed on the V-centers, desorption of the hot atoms is attributed to discharge of the surface O^- anions, and the appearance of the hot O₂ molecules is related to the associative desorption of two O^- anions localized at the same V-center discharged by a pair of excitons.