Glasses having compositions xLi(2)O center dot(85-x)Bi2O3 center dot 15SiO(2) (x=35, 40, and 45 mol%) were prepared by normal melt quenching technique. Electrical relaxation and conductivity in these glasses were studied using impedance spectroscopy in the frequency range from 20 Hz to 1 MHz and in the temperature range from 453 to 603 K. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency were extracted from the impedance spectra. The dc conductivity increases with increase in Li2O content providing modified glass structure and large. number of mobile lithium ions. Similar values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome the same energy barrier while conducting and relaxing. The non-exponential character of relaxation processes increases with decrease in stretched exponential parameter 'beta' as the composition parameter 'x' increases. The observed conductivity spectra follow a power law with exponent 's' which increases regularly with frequency and approaches unity at higher frequencies. Nearly constant losses (NCL) characterize this linearly dependent region of the conductivity spectra. A deviation from the 'master curve' for various isotherms of conductivity spectra was also observed in the high-frequency region and at low temperatures. which supports the existence of different dynamic processes like NCL in addition to the ion hopping processes in the investigated glass system. (C) 2009 Elsevier B.V. All rights reserved.