In situ polymerization of aniline was carried out in the presence of fly ash (FA) to synthesize polyaniline/ fly ash (PANI/FA) composites. The PANI/FA composites have been synthesized with various compositions (15, 20, 30 and 40 wt%) of FA in PANI. The composites, thus synthesized have been characterized by infrared spectroscopy and X-ray diffraction. The morphology of these samples was studied by scanning electron microscopy. Further the a.c. conductivity of these composites have been investigated in the frequency range 10²–10⁶ Hz. The presence of polarons and bipolarons are made responsible for frequency dependence of a.c. conductivity in these composites. The Cole-Cole plots indicate clear shift in the distribution of relaxation times as the wt% of FA in PANI changes. These composites show almost symmetric semicircles of Cole-Cole plots indicating the Debye-type relaxation in their polarization response.