Recent reports describing photoluminescence in porous silicon have heightened the level of interest in it as a unique electronic material, and have created a need for a more complete understanding of the mechanism of porous silicon formation. The various models describing porous silicon formation are reviewed and the known electrochemical and morphological properties are discussed with the intention of unifying the different models into a comprehensive explanation for the formation of a porous structure in silicon. Because the specific surface dissolution chemistry is critical for a complete understanding of pore formation, some of the more prominent dissolution reactions are also reviewed and their relative importance to pore generation and morphology is discussed. Some aspects of the recently reported quantum effects are also reviewed. Because the mechanism of porous silicon formation involves a wide range of interdisciplinary fields, a considerable number of analogies and examples to related phenomena are also presented throughout the review to aid comprehension.