Nanostructured YSZ+NiO functional layers for SOFC anodes were developed by air plasma spraying. Spray processing was controlled to conserve finely porous and nanostructure of the feedstock in the deposit. The optimized deposits exhibiting high gas permeability, suitable high temperature electronic conductivity, enhanced triple phase boundaries and catalytic activity. The results were compared with conventional NiO+YSZ and Ni-C+YSZ anodes. YSZ electrolyte layer was deposited onto the anodes for electrochemical testing at 800°C in static conditions. Impedance spectroscopy measurements were performed to collect data on the polarization resistance and catalytic behavior of these anode layers. It was established that enlarged reaction zone, provided by high specific surface area of the nanostructured anodes, and finely porous microstructure, led to lower polarizations and enhanced cell performance by more than 60% compared to conventional cells.