As a typical Ruddlesden-Popper oxide, La2NiO4+delta draws special attention for its high oxygen ion conducting behavior and special interstitial oxygen defects which enables it a promising electrocatalyst toward oxygen reduction reaction. In this work, Ca-doped La2NiO4+delta samples are prepared and their structure and defect evolution are investigated as Ca content. Electrical conductivity and electron conduction relaxation (ECR) investigations suggest that La1.9Ca0.1NiO4+delta has the great electronic conductivity and the highest oxygen surface exchange coefficient and oxygen bulk diffusion coefficient at intermediate temperatures. These results may imply that more gas oxygen has inserted into La1.9Ca0.1NiO4+delta sample, suggesting the native interstitial oxygen defects in it. X-ray photon spectroscopy (XPS) results confirm that La1.9Ca0.1NiO4+delta have more active oxygen species when compared with La2NiO4+delta and La1.8Ca0.2NiO4+delta. The great oxygen exchange and bulk diffusion properties along with its great stability in steam involved atmosphere enables it a promising for cathode for H-SOFCs. Compared with that using La2NiO4+delta cathode, peak powder density of H-SOFC using La1.9Ca0.1NiO4+delta single phase cathode improves about 30.5% at 700 degrees C, suggesting that accelerating oxygen reduction reaction can effectively improve cathode performance of H-SOFCs. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.