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To improve the performance and overcome the processing difficulties of La0.99Ca0.01NbO4 proton-conducting ceramic oxide, external and internal strategies were used, respectively, to modify La0.99Ca0.01NbO4 with NiO. The external strategy refers to the use of the NiO as a sintering aid. The NiO was added to the synthesized La0.99Ca0.01NbO4 powder as a secondary phase, which is the traditional way of using the NiO sintering aid. The internal strategy refers to the use of NiO as a dopant for the La0.99Ca0.01NbO4. Both strategies improve the sinterability and conductivity, but the effect of internal doping is more significant in enhancing both grain growth and conductivity, making it more desirable for practical applications. Subsequently, the influences of different concentrations of NiO were compared to explore the optimal ratio of the NiO as the dopant. It was found that the sample with 1 or 2 wt.% NiO had similar performance, while with 5 wt.%, NiO doping content hampered the grain growth. In addition, the inhomogeneous distribution of the element in the high-NiO content sample was found to be detrimental to the electrochemical performance, suggesting that the moderate doping strategy is suitable for La0.99Ca0.01NbO4 proton-conducting electrolyte with improved performance. Furthermore, first-principle calculations indicate the origin of the enhanced performance of the internally modified sample, as it lowers both oxygen formation energy and hydration energy compared with the un-modified one, facilitating proton migration.