The paper investigated the effect of chemical etching and temperature on the optical properties and microstructures of porous silicon layer fabricated by the pulse electrochemically etching by means of the reflectance spectroscopy and photoluminescence spectroscopy. The relationship between the optical thickness (nd) and refractive index n of porous silicon layer and the chemical etching time and temperature has been detailedly studied. With increasing the chemical etching times, the reflectance spectra exhibit the more intense interference oscillations, which mean the uniformity and interface smoothness of porous silicon layers become better, meanwhile, results in decreasing the optical thickness and refractive index, indicating a higher porosity. Moreover, the intensity of photoluminescence spectra increases, and the envelope curves of photoluminescence spectra exhibit a trend of red-shift, which implied the average diameter of silicon nanocrystallite became larger. The chemical etching rate of the optical thickness intensely increases with the chemical etching temperature.