A substrate-independent method is described for the synthesis of polymer brushes on solid surfaces. This entails pulsed plasma deposition of maleic anhydride to generate a free radical initiator containing thin film followed by styrene polymerization. Polystyrene layers of up to 150 nm thickness can be grown from these initiator surfaces. This reaction can be inhibited by exposure to a free radical scavenger, which is consistent with the proposed free radical initiator mechanism. UV irradiation through a photomask of such capped surfaces leads to localized reactivation of the initiator sites, which in turn provides a method for the microfabrication of patterned polystyrene brush surfaces.