Plasma graft polymerized styrene was formed by a reactor with a parallel plate electrode system on a pulsed plasma polymerized styrene film in a monomer vapor, where the pulsed plasma polymerization was performed by a low frequency 100%pulse modulation of 13.56 MHz power source in styrene vapor. The pulse duration was varied in the range of 0.01∼1 sec and ON time/duty cycle ratio was 1/10 and 1/20. The processes were monitored by a quartz crystal microbalance. The initial stage of plasma polymerization and grafting are discussed in this paper. Also sub 100 nm lines and spaces pattern on the resist delineated by an electron-beam pattering machine was developed by hexane.