Small (3-5 nm in diameter following HRTEM images) Si nanocrystals were produced in a two-stage process including (1) nanosecond laser ablation of a Si target in an organic liquid (chloroform) that results in formation of big composite polycrystalline particles (about 20-100 nm average diameter) and ( 2) ultrasonic post-treatment of Si nanoparticles in the presence of HF. The post-treatment is responsible for disintegration of the composite Si particles, release of small individual nanocrystals, and reduction of their size due to HF-induced etching of Si oxide. The downshift and broadening of the ∼520 cm -1 Raman phonon band of the small Si nanocrystals with respect to the bulk Si Raman band is consistent with the presence of ∼4.5 nm Si nanocrystals. The photoluminescence spectra (450-900 nm) and decay kinetics of small Si nanocrystals were detected, and the possible origin of the luminescence is discussed.