Graft copolymers of poly(vinyl alcohol) with thiophene side-groups and pyrrole were synthesized by electrochemical polymerization methods. Poly(vinyl alcohol) with thiophene side-groups (PVATh) was obtained from the reaction between poly(vinyl alcohol) (PVA) and thiophene-3-acetic acid. The syntheses of copolymers Of PVATh and pyrrole were achieved electrochemically by using three different supporting electrolytes, p-toluene sulfonic acid (PTSA), sodium dodecyl sulfate (SDS) and tetrabutylammonium tetrafluoroborate (TBAFB). Characterization of PVATh and graft copolymers was performed by a combination of techniques including cyclic voltammetry, scanning electron microscopy, thermal gravimetry, differential scanning calorimetry, size-exclusion chromatography, H-1 NMR and FT-IR. The conductivities were measured by the four-probe technique. (C) 2004 Society of Chemical Industry.