We studied the dependence of porous silicon (PS) morphology on fabrication conditions and the link between morphology, porosity and optical properties. P-type (100) silicon wafers with resistivity of 10 Omega cm were electrochemically etched in a HF:ethanol:water mixture at various HF concentrations and current densities. Porosity and thickness of the samples were determined gravimetrically. Detailed information about evolution of porous silicon layer morphology with variation of preparation conditions was obtained by scanning electron microscope (SEM), the presence of silicon nanoparticles was confirmed by high resolution transmission electron microscopy. Decrease of the mean size of silicon nanoparticles with increasing porous silicon porosity was revealed in a monotonous blue shift of photoluminescence (PL) maximum in room temperature photoluminescence spectra of studied samples. This blue shift is consistent with quantum confinement model of photoluminescence mechanism. We observed that total porosity of porous films cannot fully explain observed photoluminescence behavior and correct interpretation of the blue shift of photoluminescence spectra requires detailed knowledge of porous silicon morphology. (C) 2004 Elsevier B.V. All rights reserved.