This study investigates the novel cobalt‐free high‐entropy perovskite, La0.2Pr0.2Nd0.2Sm0.2Sr0.2FeO3–δ (LPNSSF), as an air electrode material for solid oxide cells (SOCs). When testing a button cell with a single‐phase LPNSSF electrode, a current density of 0.55 A cm−2 is obtained at 0.7 V in fuel cell mode at 800°C. In order to mitigate the moderate electronic conductivity of LPNSSF, two approaches are explored. Incorporating a Co‐free highly conductive perovskite, LaNi0.6Fe0.4O3–δ (LNF), either as an LPNSSF–LNF composite electrode or as a current collector layer (CCL), enhances the performance to 0.61 and 0.66 A cm−2, respectively, under the same conditions. Microstructural features are studied by electron microscopy and show a rather dense structure of the CCL. Optimization of the current collector increases the current density further to 0.96 A cm−2 at 0.7 V in a 5 × 5 cm2 anode‐supported cell at 800°C. This cell exhibits good long‐term stability in electrolysis mode in H2‐H2O with 80% humidification. Continuous polarization of −0.69 A cm−2 is sustained for 1000 h, with an average degradation rate of 10 mV kh−1 after an initial run‐in phase. These findings demonstrate the promising performance and durability of LPNSSF as cobalt‐free SOC air electrode.