Benzoylated polystyrene (BPS) was subjected to UV radiation in solution in the presence of isopropanol where upon, it was observed to undergo essentially quantitative crosslinking to form polystyrene resin with tertiary hydroxyl functionality. The crosslinking kinetics was followed by IR spectroscopy. The desired degree of crosslinking was accomplished by controlling the extent of benzoylation of the polymer. Following crosslinking, the gels were freeze-dried and suitably characterized by solid state NMR and IR spectroscopic techniques. Scanning electron microscopic studies reveal the formation of porous network. Some of the crosslinked resins, dried suitably, exhibit high surface area as confirmed by BET adsorption isotherm studies.