Here we prepared vertical and single crystalline porous silicon nanowire (SiNW) arrays using the silver-assisted electroless etching method. The selenization was carried out by annealing the samples in vacuum with selenium atmosphere. The selenization treatment at 700 °C is useful for investigating the photoluminescence (PL) properties of porous SiNWs, with an enhancement of 30 times observed. The observed PL peaks blue-shift to 650 nm and the decomposition of the spectrum reveals that three PL bands with different origins are obtained. It is proved that selenization treatment could remove the Si-H bonds on the surface and form Si-Se bonds, which could increase the absorbance of the SiNWs and also enhance the stability of the PL intensity. These Se-treated porous SiNWs may be useful as nanoscale optoelectronic devices.