The origin and stability of luminescence are critical issues for Si nanocrystals which are intended for use as biological probes. The optical luminescence of alkyl-monolayer-passivated silicon nanocrystals was studied under excitation with vacuum ultraviolet photons (5.1–23 eV). Blue and orange emission bands were observed simultaneously, but the blue band only appeared at low temperatures (8.7 eV). At 8 K, the peak wavelengths of the emission bands were 430±2 nm (blue) and 600±2 nm (orange). The orange and blue emissions originate from unoxidized and oxidized Si atoms, respectively.