Hexagonal Se nanowires were synthesized using a simple vapor-phase growth with the assistance of the silicon powder as a source material, which turned out to be very important in the growth of the Se nanowires. The morphology, microstructure, and chemical compositions of the nanowires were characterized using various means (XRD, SEM, TEM, XPS, and Raman spectroscopy). The possible growth mechanism of the Se nanowires was explained. The as-grown Se nanowires may find wide applications in biology and optoelectronics.