Glasses in the system CaO–Bi2O3–B2O3 (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond–West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent β (0.5–0.6) is invariant with temperature for the present glasses.