Solid oxide fuel cell positive-electrolyte-negative (SOFC PEN) structures were fabricated by complex tape casting and co-firing technologies. La0.8Sr0.2FeO3 (LSF20) powders for cathode and 8 mol% yttria-stabilized zirconia (YSZ) powders for electrolyte were synthesized through glycine-nitrate process (GNP). The slurries for cathode, electrolyte and anode (NiO-YSZ) were cast in sequence to form green PEN structures. Co-fired at 1200oC for 6 h, there were no delamination, crack or curl occurred in PEN structures. SEM analysis showed that YSZ electrolyte film had been sintered to full dense and the interface combinations were compact. No evident reaction product between YSZ and LSF20 was detected by XRD.