N-isopropylacrylamide was successfully polymerized on silicon disc surfaces at room temperature by interface-mediated dissociative electron transfer reversible addition-fragmentation chain transfer (IMDET-RAFT) polymerization. The IMDET-RAFT technique was used for the first time to synthesize polymer brushes with a new mechanism using inorganic sulfides without using metal at room temperature. The polymerization was well controlled and the PNIPAAm brushes were successfully grown on silicon disc surfaces. The presence of sulfur atoms at the chain end was demonstrated by XPS experiments to demonstrate the controlled nature of the polymerization. Polymer brushes synthesized by IMDET-RAFT technique have high grafting density and grafting density was found to be 0.76 chain/nm(2). This study is thought to be an important alternative to the new generation controlled/living polymerization, especially for RAFT polymerization techniques used in polymer brush synthesis. PNIPAAm brushes synthesized with IMDET-RAFT technique are an important starting point for future studies in terms of the synthesis of polymer brushes with IMDET-RAFT technique using a wide range of monomers both at ambient temperature and metal free. It is believed that this technique has the potential to be used in the future, especially in the preparation of temperature sensitive surfaces, bio-application studies and many surface modifications.