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Nickel (Ni)–8 mol% yttria stabilized zirconia (YSZ) cermet prepared through novel electroless technique is used as solid oxide fuel cell anode. The developed anode (28 vol% Ni) is used in two different configurations, viz. anode support and anode active layer (AAL). Highest electrochemical performance of 3.2 A/cm2 with lowest cell area specific resistance (∼94 mΩ cm2) at 800°C is obtained from anode-supported single cell having an optimized 15 μm electroless AAL. Electrochemical performances are correlated with anode pore-size distributions. Such high performance cells also exhibit significant low degradation rate (∼2% 1000 h−1 at a load 0.5 A/cm2) during long-term testing.