Substituted polyaniline/chitosan (sPANI/Ch) composites were chemically synthesized in H2SO4 and CH3COOH synthesis media. Structural and physical properties of the composites were characterized by using FTIR, SEM, TGA, UV-vis, XRD techniques, and conductivity measurements. The effect of synthesis media on morphology, thermal stability, conductivity, and crystalline properties was investigated. Chemical interactions between substituted polyanilines and chitosan were explained using FTIR spectra results. The different morphological surfaces were observed in SEM images of the composites. The size of the substituted polyaniline/chitosan (sPANI/Ch) composites was in nanoscale, and the composites synthesized in acetic acid media showed smaller structures than those of H2SO4 media and pure chitosan. It was interpreted from XRD results that the composites have amorphous structure and the PNEANI/Ch-CH3COOH composite has the highest crystallinity. (C) 2011 Elsevier Ltd. All rights reserved.