The effects of experimental conditions (i.e., flow rate, pressure, discharge wattage, and glow characteristics) on the plasma polymerization of acrylonitrile were investigated. It was found that the glow characteristic is highly dependent on both flow rate and discharge wattage and that the plasma polymerization depends strongly on the glow characteristic. However, when experimental conditions are selected to maintain a fully developed glow in the tail flame portion of rf discharge, plasma polymerization is independent of discharge wattage and pressure. The polymer deposition rate is linearly proportional to the monomer flow rate. The deviations from this ideal situation are generally attributable to incomplete glow or partial glow under conditions which caused the deviation. The “character” of the glow largely determines the chemistry of the system. Consequently, the properties of polymers formed under different glow characteristics are also different.