New functional polymeric, semiconducting materials were synthesized by chemical oxidative polymerization of acriflavine hydrochloride in aqueous solution at room temperature, using ammonium peroxydisulfate as an oxidant. Polymerization products were characterized by gelpermeation chromatography (GPC), FTIR spectroscopy, scanning electron microscopy (SEM) and conductivity measurements. The influence of the oxidant/monomer molar ratio on the molecular structure, molecular weight distribution and the electrical conductivity of polyacriflavines was studied. Molecular weights approach a maximum value of ~20000. The polyacriflavine prepared by using oxidant/monomer molar ratio 1.25 shows the conductivity of 2.8 × 10–7 S cm–1. New substitution pattern shown by FTIR spectroscopic analysis combined with MNDO-PM3 semiempirical quantum chemical calculations revealed N─C2 coupling reactions as dominant. The formation of phenazine rings in ladder structured polymerization products was observed by FTIR spectroscopy. The existence of a certain polyacriflavine crystalline structure was suggested from the SEM micrographs.