Porous silicon has received considerable attention lately due to its unique optical properties and use in sensor applications. The utility of this material can be further advanced with the aid of new surface chemical modification methods. Here we describe two transition metal mediated reactions that allow for the mild and chemoselective functionalization of porous silicon. The first method utilizes rhodium carbene chemistry to modify porous silicon surfaces with esters and amides. The second technique exploits a pt-based Karstedt's catalyst to affect the hydrosilylation of porous silicon with alkenes. The mildness and selectivity of the hydrosilylation is highlighted by modification of n-type porous silicon matrix with an 8-residue cyclic peptide.