Polymers from azulene (A) and 2-[(E)-2-azulen-1-ylvinyl]thiophene (B) electrochemically synthesized are materials with a broad absorbance in the UV-vis spectral region. An experimental approach to correlate the Raman and in situ FTIR spectra from azulene based polymers according to the effective conjugation coordinate theory (ECC) is presented. Film characterization was made by Raman and Fourier transform infrared attenuated total reflectance, FTIR-ATR spectroscopy. Throughout the whole work A was used as a model compound. The polymers were synthesized at different polymerization potentials in order to create different structures. Polyazulene showed a divergent Raman response upon change in excitation wavelength, lambda(exc)= 514 nm and lambda(exc)= 780 nm, in comparison to common conducting polymers. The FTIR-ATR measurements were made during charging-discharging of the polymers. The IR spectra of the conducting state show new doping induced infrared active vibrations (IRAV) in the region between 1600 and 700 cm(-1) and a broad electronic absorption in the high energy range (4000-8000 cm(-1)). Two different structures of the polymer from B are formed, and both follow the trends for conducting polymers upon charging.