The potential of the perovskite system Nd1–xSrxCoO3−δ(x= 1/3 and 2/3) as cathode material for solid oxide fuel cells (SOFCs) has been investigated via detailed structural, electrical, and electrochemical characterization. The average structure of x= 1/3 is orthorhombic with a complex microstructure consisting of intergrown, adjacent, perpendicularly oriented domains. This orthorhombic symmetry remains throughout the temperature range 373–1073 K, as observed by neutron powder diffraction. A higher Sr content of x= 2/3 leads to stabilization of the cubic perovskite with a homogeneous microstructure and with a higher oxygen vacancy content and cobalt oxidation state than the orthorhombic phase at SOFC operation temperature. Both materials are p-type electronic conductors with high total conductivities of 690 and 1675 S·cm–1at 473 K in air for x= 1/3 and 2/3, respectively. Under working conditions, both compounds exhibit similar electronic conductivities, since x= 2/3 loses more oxygen on heating than x= 1/3, associated with a greater loss of p-type charger carriers. However, composite cathodes prepared with Nd1/3Sr2/3CoO3−δand Ce0.8Gd0.2O2−δpresent lower ASR values (0.10 Ω·cm2at 973 K in air) than composites prepared with Nd2/3Sr1/3CoO3−δand Ce0.8Gd0.2O2−δ(0.34 Ω·cm2). The high activity for the oxygen electrochemical reaction at intermediate temperatures is likely attributable to a large disordered oxygen-vacancy concentration, resulting in a very promising SOFC cathode for real devices.