Proton exchange membrane (PEM) is synthesized successfully by plasma polymerization technique in RF plasma discharge. The chemical composition of the prepared membranes is examined by FTIR analyses. SEM and AFM analysis of the membrane show the formation of a prominent pillar surface structure at high RF power. The pillar structure of the membrane also plays an indispensable role in the cell performance of the plasma polymerized PEM. The physical properties of the membrane developed under different plasma conditions are investigated in the range of RF power from 20 to 80 W. The membrane synthesized at 50 W shows better cell performance that it develops 610 mW cm(-2) of power density and 0.68 A cm(-2) of current density at 0.6 volts in fuel cell than other membranes synthesized at different plasma conditions.