This research focuses on the syntheses of polyaniline with poly(styrenesulfonic acid) and their electrochemical behavior, including absorbance behavior and electrochemical response time of polyaniline-poly(styrenesulfonic acid) [PANI-PSSA]. The complexes PANI-PSSA were prepared by electrochemical polymerization of monomer (aniline) with PSSA, using indium-tin oxide (ITO) as working electrode in 1M HCl solution. Polyaniline (PANI), poly(o-pheneddine)poly(styrenesulfonic acid) [POP-PSSA], and poly(2-ethylaniline)-poly(styrenesulfonic acid) [P2E-PSSA] also were prepared by electrochemical polymerization and to be the reference samples. The products were characterized by IR, VIS, EPR, water solubility, elemental analysis, conductivity, SEM, and TEM. IR spectral studies shows that the structure of PANI-PSSA complexes is similar to that of polyaniline. EPR and visible spectra indicate the formation of polarons. The morphology of the blend were investigated by SEM and TEM, which indicate the conducting component and electrically conductive property of the polymer complexes. Elemental analysis results show that PANI-PSSA has a nitrogen to sulfur ratio (N/S) of 38%, lower than that for POP-PSSA (52%) and P2E-PSSA (41%). Conductivity of the complexes are around 10(-2) S/cm, solubility of PANI-PSSA in water is 3.1 g/L. The UV-Vis. absorbance spectra of the hybrid organic/inorganic complementary electro-chromic device (ECD), comprising a polyaniline-poly(styrenesulfonic acid) [PANI-PSSA] complexes and tungsten oxide (WO,) thin film coupled in combination with a polymer electrolyte poly(2-acrylamido-2-methyl-propane-sulfonic acid) [PAMPSA]. PANI-PSSA microstructure surface images have been studied by AFM. By applying a potential of similar to 3.0 V across the two external ITO contacts, we are able to modulate the light absorption also in the UV-Vis region (200900 nm) wavelength region. For example, the absorption changes from 1.20 to 0.6 at 720 run. The complexes PANI-PSSA, POP-PSSA, and P2E-PSSA were prepared by electro-chemical polymerization of monomer (aniline, o-phenetidine, or 2-ethylaniline) with poly(styrenesulfonic acid), using ITO as working electrode in 1M HCl solution, respectively. UV-Vis spectra measurements shows the evidences for the dopped polyaniline system to be a highly electrochemical response time, recorded at the temperature 298 K, and the results were further analyzed on the basis of the color- discolor model, which is a typical of protontation systems. Under the reaction time (3 s) and monomer (aniline, o-phenetidine, 2-ethylaniline) concentration (0.6M) with PSSA (0.15M), the best electrochemical color and discolor time of the PANT-PSSA is slower than POP-PSSA complexes (125/125 ms; thickness, 3.00 mu m) and P2E-PSSA complexes. Under the same thickness (10 Am), the best electrochemical color and discolor time of the PANT-PSSA complexes is 1500/750 ms, that is much slower than P2E-PSSA complexes (750/500 ms) and POP-PSSA complexes (500/250 ms). In film growing rate, the PANI-PSSA complexes (0.54 mu m/s) are slower than P2E-PSSA complexes (0.79 mu m/s) and POP-PSSA complexes (1.00 mu m/s), it can be attributed to the substituted polyaniline that presence of electro-donating (-OC2H5 or -C2H5) group present in aniline monomer. The EPR spectra of the samples were recorded both at 298 K and 77 K, and were further analyzed on the basis of the polaron-bipolaron model. The narrower line-width of the substituted polyaniline complexes arises due to polarons; i.e. , it is proposed tha charge transport take place through both polarons and bipolarons, compared to their salts can be attributed to the lower degree of structural disorder, the oxygen absorption on the polymeric molecular complexes, and due to presence of electro-donating (-OC2H5 or -C2H5) group present in aniline monomer. (c) 2006 Wiley Periodicals, Inc.