Detailed in situ absorption spectral investigation of chemical oxidative polymerization of aniline in dodecylbenzene sufonic acid (DBSA) based system revealed that the chain propagation is assisted by redox equilibrium intermediate (REI) rather than a fully oxidized pernigraniline. The continuous reduction (addition of aniline) and oxidation (by oxidant) of REI, propagate the chain. The polymerization process consists of three prominent stages called induction period (IP), chain propagation and termination. The initial stage of polymerization is realized as IP, the time taken to establish REI. The presence of fully developed polaron band indicates REI has delocalized structure. Invariant spectral features together with tremendous increase in absorbance at propagation phase indicate REI undergoes reductive addition of aniline and oxidation by APS (ammonium persulfate) while maintaining equilibrium structure. The greatly increased absorbance with time at this stage is due to well-known autoacceleration phenomenon observed for aniline polymerization. The increase in redox potential of REI with increase in chain length accelerates the reaction and accounts for autoacceleration. The termination of polymerization would be reduction or oxidation depending on the availability of aniline or oxidant respectively. In a system where the oxidant is the limiting agent, reduction continues until it reaches emeraldine salt that is incapable of further reduction. On the other hand an excess of oxidant, results in the formation of pernigraniline by continuous oxidation. (C) 2004 Elsevier Ltd. All rights reserved.