An amorphous silicon nanowire (a-SiNW) array perpendicular to a glass substrate can be successfully obtained through the metal-assisted chemical etching of amorphous silicon (a-Si) thin films. The solid-phase crystallization of a-SiNWs was carried out by thermal annealing in a forming gas in the temperature range from 600 to 900 °C. The effects of hydrogen in the film and the film morphology on the crystallization of a-SiNWs were investigated by Raman spectroscopy and transmission electron microscopy. A higher hydrogen concentration of a-SiNWs reduced the crystallization temperature, as in a-Si thin films. It was also revealed that the large surface area of the a-SiNW array affected the crystallization process. We also studied the optical property of the fabricated SiNW array and demonstrated its high potential as an active layer in solar cells.