Semiconductor selenides of MSe (M = Cd, Hg) nanocrystalline powders were synthesized through the reactions between metal chlorides and sodium selenosulfate in the ammoniacal aqueous solution at room temperature for 6–10 h. The samples were characterized by x-ray powder diffraction, transmission electron microscopy, electron diffraction, x-ray photoelectron spectroscopy, and elemental analysis. The average diameters of CdSe and HgSe nanocrystallites are 4 and 8 nm, respectively. The storage and an interesting phase transition under hydrothermal conditions have been presented. The absorption spectrum of the as-prepared samples exhibits obvious blue shift due to the size confinement.