Despite the great potential of solid oxide electrochemical cells (SOCs) as highly efficient energy conversion devices, the undesirable high operating temperature limits their wider applicability. Herein, a novel approach to developing high-performance low-temperature SOCs (LT-SOCs) is presented through the use of an Er, Y, and Zr triple-doped bismuth oxide (EYZB). This study demonstrates that EYZB exhibits > 147 times higher ionic conductivity of 0.44 S cm(-1) at 600 degrees C compared to commercial Y-stabilized zirconia electrolyte with excellent stability over 1000 h. By rationally incorporating EYZB in composite electrodes and bilayer electrolytes, the zirconia-based electrolyte LT-SOC achieves the unprecedentedly high performance of 3.45 and 2.02 W cm(-2) in the fuel cell mode and 2.08 and 0.95 A cm(-2) in the electrolysis cell mode at 700 degrees C and 600 degrees C, respectively. Further, a distinctive microstructural feature of EYZB that largely extends triple phase boundary at the interface is revealed through digital twinning. This work provides insights for developing high-performance LT-SOCs.