Abstract Dc and ac conductivities of Li 2O–BaO–Bi 2O 3 glasses have been studied in a temperature range of 263–523 K and a frequency range of 10 Hz–2 MHz and have been compared with those of binary Li 2O–Bi 2O 3 glasses. The frequency dependent conductivity has been studied employing both the modulus and conductivity formalisms. We have observed small changes in the dc conductivity and its activation energy from those of the binary glass when content of BaO is small. However we have observed noticeable changes in the conductivity and the activation energy when BaO content is large. The significant changes in the values of the non-exponential parameter and the power-law exponent of the ac electrical properties have been observed due to introduction of BaO in the lithium bismuthate glasses. The existing relation between the power-law exponent and the non-exponential parameter was also violated in the present glass compositions.