Water-soluble, electrically conductive polyaniline (PANI)-poly(vinyl alcohol) (PVA) blends of different compositions (10, 30, 50, and 70 w/w) were synthesized by emulsion and inverted emulsion methods with ammonium persulfate and benzoyl peroxide as the oxidants, respectively, with PANI protonated with sulfosalicylic acid. The absorption, Fourier transform infrared, Fourier transform Raman, NMR, and electron paramagnetic resonance (EPR) spectroscopic studies suggested chemical interaction between PANI and PVA. The morphology of the blends depended on the method of synthesis as observed from scan-ning electron microscopy, X-ray diffraction, and particle size measurements. The blends showed relatively improved mechanical strengths but had lower degradation temperatures than the PANI salt and displayed conductivities as high as 10(-2) to 10(-1) S/cm. The blends synthesized by the inverse emulsion method had smaller particle sizes, higher crystallinities, and better mechanical properties. (c) 2005 Wiley Periodicals, Inc.