During the last three decades, a large number of investigations has been reported pertaining to the science and technology of solid oxide fuel cells (SOFCs) based mainly on the yttria-stabilized zirconia (YSZ) electrolyte. Because of the problems associated with the high temperature of operation (approximately 1000-degrees-C) of the YSZ-based cells, there has been a substantial effort to develop alternative electrolytes with ionic conductivity comparable to that of YSZ at relatively lower temperatures. This review presents a systematic evolution in the area of the development of new electrolytes based on bismuth sesquioxide for fuel cell applications at moderate temperatures.