A novel conductive blend of polyaniline (PANI) with polyamidoamine dendrimer (PAMAM (G 2-0)) was prepared by different blending procedure. The PANI-PAMAM blended polymers were characterized by UV-vis, FTIR, and electron paramagnetic resonance (EPR) spectra. The effect of varying the blending procedure on structure and EPR properties of PANI-PAMAM blended polymers was investigated. Varying the blending procedure and temperature has a direct effect on the structure and EPR parameters (Delta Hpp, g factor, N-S, T-2, and A/B ratio). EPR spectroscopic studies suggested the presence of chemical interaction between PANI and PAMAM. Electron localization effects in PANI-PAMAM blended polymers can therefore be studied using the technique of EPR. (c) 2005 Wiley Periodicals, Inc.