This paper is focused on the formation mechanisms and the general behavior of negative ions in low pressure radio-frequency (RF) plasmas operated in a mixture of argon and aniline vapor. This type of plasma is mostly used for the synthesis of polyaniline, one of the most studied conductive polymers. Experiments based on mass spectroscopy measurements reveal the necessity to have a thin layer of plasma synthesized polyaniline on the electrodes to produce negative ions through complex surface reactions. In addition, thin-films deposited using this type of discharge are analyzed by means of Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS). The material analysis gives a first indication about the possible contribution of negative ions to polyaniline deposition.