The striking photoluminescence properties of porous silicon have attracted considerable research interest since their discovery in 1990. Luminescence is due to excitonic recombination quantum confined in Si nanocrystals which remain after the partial electrochemical dissolution of silicon. Porous silicon is constituted by a nanocrystalline skeleton (quantum sponge) immersed in a network of pores. As a result, porous silicon is characterized by a very large internal surface area. This internal surface is passivated but remains highly chemically reactive which is one of the essential features of this new and complex material. We present an overview of the experimental characterization and theoretical modeling of porous silicon, from the prepa...