It was observed that some water soluble products were formed during the electrochemical synthesis of polyaniline, and Raman spectroscopy can be used to detect those products. The amount of water soluble products increases with increasing electrolysis potential and the peak observed at 1620 cm(-1) is characteristic for these products. Rinsing the polyaniline coated electrode with water even once removes the soluble products from the polymer, which indicates that care must be taken in polyaniline characterization studies during washing, solvation and doping-undoping processes. The transition of H2SO4-doped polyaniline to undoped form by treating with 1.0 M NaOH takes place very rapidly in high yields which can be followed by in situ Raman spectroscopy.