We have investigated the effects of chemical etching on Raman spectra of porous silicon. The as-anodized porous silicon consisted mainly of crystalline silicon, as indicated by the Raman spectra. The background in the spectrum was strong, indicating that the porous silicon surface was rough due to the presence of pores. When chemical etching was performed five times, the Raman spectrum revealed the presence of spherically shaped nanocrystalline silicon whose diameter was around 3.5 nm. Further chemical etching, however, extinguished the nanocrystallites, in addition to smoothing the surface morphology.