Results of studies of the photoluminescence of porous silicon with different prehistories have revealed the mechanism and nature of the instability of the luminescence properties of freshly prepared samples. It was established that the initial quenching and subsequent rise of the photoluminescence is attributable to the intermediate formation of silicon monoxide (photoluminescence degradation) and subsequent additional oxidation to form SiO2 (photoluminescence rise). Ultraviolet laser irradiation accelerates this process by a factor of 200–250 compared with passive storage of the samples in air. Plasma-chemical treatment in an oxygen environment merely results in a subsequent rise in the photoluminescence as a result of the formation of monoxide on the porous silicon surface. A kinetic model is proposed for this process.