SynopsisCrosslinked networks of butyl rubber [polyisobutylene (PIB) with 2 mol % unsaturation] were swelled with various amounts of styrene containing 0.25-4.6 wt % benzoyl peroxide as initiator. Polymerization of the styrene in situ, by increase in temperature, gave novel elastomeric composites. Scanning electron micrographs suggest phase separation which is locked in at the microscopic level, with no evidence for the particulate domains seen in the similarly prepared polystyrene-polydimethylsiloxane system. The wt % polystyrene (PS) extractible increased with increase in initiator concentration, which is consistent with decrease in the lengths of the PS chains being formed and grafted onto the PIB. Mechanical properties obtained in continuous extension showed maxima in their dependence on composition. Specifically, the ultimate strength ( / / A * ) , , maximum extensibility cr, energy E, required for rupture, and permanent set AL/L, generally showed maxima in the vicinity of 50 wt % PS. The shortest-chain PS samples generally showed the largest values of ( / / A * ) , , c r , and E,, and the smallest values of AL/L,.