ABSTRACTAlkyl-terminated Si nanocrystals (NCs) are synthesized at room temperature by hydride reduction of SiCl₄ within inverse micelles. Highly monodisperse Si NCs (2 – 6 nm) are produced by variation of the cationic quaternary ammonium salts used to form the inverse micelles. Transmission electron microscopy imaging confirms the NCs are highly crystalline, while FTIR spectra confirm that the NCs are passivated by covalent attachment of alkanes, with minimal surface oxidation. The photoluminescence intensity of the Si NCs exhibits an inverse relationship with the mean NC diameter, with a quantum yield of 12 % recorded for 2 nm NCs.