In this work, low polarization resistance heterostructure cathode is constructed through (Ni,Fe) exsolution from Sr0.95Ti0.3Fe0.6Ni0.1O3-δ and following in-situ re-oxidation and precipitation as (Ni,Fe)O nano particles. The heterostructure effectively promotes oxygen reduction reaction, and decreases polarization resistance by ~50% with smallest Rp of 0.084 Ω cm2 at 700 °C, which is among the better Cobalt & Lanthanide-free cathodes. Moreover, the cathode performance is prominently optimized under low temperatures and low oxygen partial pressures, yielding smaller activation energy and lower oxygen partial pressure dependence (Rp,650°C∝(pO2)0.28). Further, the heterostructure cathode is successfully fabricated in Ni–Fe supported Solid Oxide Fuel Cell, using “whole-cell-reduction” and “cathode re-oxidation” strategies. The cell exhibits maximum electrical power density of 740 mW/cm2 at 750 °C, with Ni-YSZ anode and YSZ electrolyte. Electrical efficiencies over ~90% at operation potential above 0.75 V are obtained, showing highly efficient operation in wide range of temperatures. This is a successfully trial by coupling low-cost and high-performance cathode with metal supported Solid Oxide Fuel Cell.