The multicomponent proton conducting ceramics (STZP) and with three different compositions (STZPBi3, STZPBi10, and STZPBi15) were synthesized via a wet chemical route. These prepared materials showed good thermal stability up to around by TG/DTA analyses. Introduction of optimum quantity of bismuth as a sintering aid into the samples contributed to enhance the densification of microstructure, which is essential for the utilization of proton conducting ceramics in fuel cells operated at elevated temperature. The proton conductivity of STZP was at and that of STZPBi10 was at . The fuel cell performances using STZP and STZPBi10 were implemented at and up to , respectively. The maximum power density was at for the STZP sample and at for the STZPBi10 sample under wet hydrogen and dry oxygen. The reduction of CO poisoning on platinum catalyst was demonstrated in fuel cell operating at temperatures of , , and .