Polycrystalline sample of (Na0.5Bi0.5)ZrO3 was prepared using a high-temperature solid-state reaction technique. XRD analysis indicated the formation of a single-phase orthorhombic structure. Dielectric study revealed the diffuse phase transition at 425 degrees C. AC impedance plots were used as tools to analyse the electrical behaviour of the sample as a function of frequency at different temperatures. The ac impedance studies revealed the presence of grain boundary effect at and above 350 degrees C. Complex impedance analysis indicated non-Debye type dielectric relaxation and negative temperature coefficient of resistance (NTCR) character of (Na0.5Bi0.5)ZrO3. AC conductivity data were used to evaluate the density of states at Fermi level and activation energy of the compound. DC electrical and thermal conductivities of grain and grain boundary have been assessed.