A new type of reactor for plasma polymerization was developed in order to achieve an effective control of styrene polymerization process. Electrons and ions were extracted from the radio frequency (rf) glow discharge region to the downstream region to generate plasma polymerization. The energy of extracted ionized particles was controlled by the bias voltage of a screen grid unit. Deposited polymer thin films were analyzed by X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. The result showed that the polarity and energy of the extracted particles had considerable effect on the deposition rate and structure of the deposited films. At each bias polarity there was a maximum deposition rate vs. voltage magnitude, and the maximum at the positive voltage was higher. In addition, the bulk aromaticity of the film deposited at the negative bias was lower than at the positive bias; the surface aromaticity of the films was much higher than that of the films prepared by usual rf discharge.