Microwave-assisted surface-initiated radical polymerization (μW-SIP) is demonstrated for the rapid synthesis of polymer brush surfaces on two-dimensional substrates. μW-SIP is carried out at constant temperature and microwave power allowing comparison with conventional SIP carried out in an oil bath at the same effective solution temperature. We show μW-SIP enables significant enhancements (up to 39-fold increase) in brush thickness at reduced reaction times for a range of monomer types (i.e. acrylamides, acrylates, methacrylates, and styrene). The effects of reaction time, monomer concentration, and microwave power on film thickness are explored.