The electrical and the dielectric response of synthesized hydroxyapatite (HA) and Cr doped HA samples are obtained by impedance spectroscopy analysis. Variation in conductivity of materials was associated with the mutual interaction of Cr(III) and Cr(IV) with OH vacancies. The observed έ_LF and έ_HF dispersions of log έ vs log(f) spectra of HA and Cr-HA-100 are related to dipolar relaxations of H+ and OH− ions. The interfacial polarization is responsible for the colossal magnitude of dielectric constant and dielectric loss. This study suggests that the controlled ionic conduction, microstructure, and interfacial effects could produce excellent electrical and dielectric properties.