Intermediate-temperature solid oxide fuel cells (IT-SOFCs) have attracted attention due to their potential to overcome the trade-off between the performance and lifetime of SOFC devices. However, the guiding principle for effective material design, which can reduce operating temperatures and overcome performance decreases caused by excessive overpotential on the anode surface, has not been clearly established. In the present work, we studied the reported Schottky anomaly, which has been observed exclusively in yttria-stabilized zirconia (YSZ). To investigate this phenomenon, a small amount (less than 1200 ppm) of trivalent cations (Rh³⁺ or Fe³⁺), chemically similar to Y³⁺ in Y₂O₃, was doped onto the YSZ surface in the anode layer. Then, the current density observed from the SOFC device at 973 K was found to be nine-times higher than the SOFC device with an undoped anode. The surface first-principles calculations in the present work indicate that this performance enhancement is caused by the delocalized electrons induced by trivalent cation doping in the vicinity of the three-phase boundary and the promotion of surface oxygen diffusion in YSZ. Based on all experimental data, the effective material design guiding principle was obtained for utilizing the unique physical property of YSZ for applications such as IT-SOFCs.