We studied the effect of surface roughness of Si wafers on porous silicon by means of photoluminescence (PL), Fourier transformed infrared (FTIR) absorption and Raman spectroscopy. We prepared several kinds of Si wafers with a different surface roughness, and then the anodization was performed at a same condition. PL spectra show a blue shift with the increase of surface roughness. The particle size of porous silicon nanostructure becomes the smaller with increasing surface roughness at the same time. On the other hand, FTIR absorption spectra show no difference regardless of surface roughness. The PL emission dependent on the surface roughness originates from a quantum size effect. We infer that the surface roughness causes the concentration of the current during anodization in the area where the radius of the curvature at the surface is small.