We report on the photosensitizing properties of optically excited Silicon (Si) nanocrystal assemblies that are employed for an efficient generation of singlet oxygen. Spin triplet state excitons confined in Si nanocrystals transfer their energy to molecular oxygen (MO) adsorbed on the nanocrystal surface. This process results in a strong suppression of the photoluminescence (PL) from the Si nanocrystal assembly and in the excitation of MO from the triplet ground state to singlet excited states. The high efficiency of the energy transfer if favored by a broad energy spectrum of photoexcited excitons, a long triplet exciton lifetime and a highly developed surface area of the nanocrystal assembly. Due to the specifics of the coupled system Si nanocrystal – oxygen molecule all relevant physical parameters describing the photosensitization process are accessible experimentally. This includes the role of resonant and phonon-assisted energy transfer, the dynamics of energy transfer, and its mechanism.