In this study, porous silicon films are fabricated by electrochemical etching on crystalline silicon substrates that result in microstructures. Teflon is used as the electrochemistry etching container. The ethyl alcohol and HF solutions are mixed with glucose to fabricate the porous silicon structure. In addition, the SEM is used to observe the morphology of porous silicon film. The performance of photoluminescence is also measured. Such results are compared with the traditional methods whose solutions have no glucose inside. It is found that the glucose helps the electrochemical etching remarkably.