The influence of binary mixtures of alcohols with different diluents on the porous structure of styrene-divinylbenzene (Sty-DVB) copolymers was investigated. Two series of binary mixtures were tested : one with isoamyl alcohol (i-AmA) and another with benzyl alcohol (BA). For systems containing i-AmA, the hydrogen bonds between alcohol and polar solvent molecules exert strong precipitating effects. Copolymers prepared with polar solvent/i-AmA presented higher porosities than copolymers obtained in presence of nonpolar solvent/i-AmA. Binary mixtures with i-AmA produced more porous and rigid networks than with BA.