In situ polymerization of pyrrole was carried out in the presence of fly ash (FA) to synthesize polypyrrole-fly ash composites (PPy/FA) by chemical oxidation method. The PPy/FA composites have been synthesized with various compositions (10, 20, 30, 40 and 50 wt%) of fly ash in pyrrole. The surface morphology of these composites was studied with scanning electron micrograph (SEM). The polypyrrole-fly ash composites were also characterized by employing X-ray diffractometry (XRD) and infrared spectroscopy (IR). The a.c. conductivity behaviour has been investigated in the frequency range 102–106 Hz. The d.c. conductivity was studied in the temperature range from 40–200°C. The dimensions of fly ash in the matrix have a greater influence on the observed conductivity values. The results obtained for these composites are of greater scientific and technological interest.