This article describes a polymer-controlled chemical method for synthesis of trigonal selenium (t-Se) nanowire bundles in the presence of poly(vinyl alcohol) (PVA) at 100 degrees C. Electron microscope images show that Se nanowires have diameters of 30-50 nm and lengths of up to a few tens of micrometers. TEM images display the direct evidence for the growth process of single-crystalline Se nanowire bundles, which suggested that Se nanowire bundles were directly converted from the initial amorphous Se micro-particles in the presence of PVA. UV-Vis absorbance of t-Se nanowire bundles revealed that the bandgap and absorbance peaks displayed larger blue shifts relative to those of bulk t-Se.