Hexagonal cadmium selenide (CdSe) nanowires, with diameter around 20 nm, were synthesized using a simple vapor-phase growth. Silicon (Si) powder acts as a source material assisting the synthesis, which is very important to the formation of the CdSe nanowires. We also suggest that self-catalysis at the Cd-terminated (0001) surface, together with the assistance action of Si, leads to the formation of wire-like structures to be formed. Meanwhile, the assistance of Si is responsible for the fineness and uniformity of the CdSe nanowires. The possible growth mechanism of the CdSe nanowires is proposed, and the optical property of the as-grown CdSe nanowires is characterized.