CdS was synthesized by solvothermal reaction of CdCl2.2.5H2O and (NH2)2CS in ammonia solution at 200 oC for 10 h. XRD, TEM and SAED show that the products are nanocrystalline CdS. The phase is 100 % hexagonal (hcp) in pure water, gradually transformed into cubic with the increase of NH3 concentration, and 100 % cubic in 25 % NH3 solution. By using FTIR, no solvents were detected in the products. Raman analysis revealed the presence of 1LO (longitudinal optical) and 2LO phonon peaks at 297.0 and 597.1 cm-1 for CdS (hcp), and 295.9 and 596.9 cm-1 for CdS (cubic), respectively. Strong peaks of the photoluminescent (PL) spectra were detected at 450 nm for hcp, and 519 nm for cubic.