The poor electronic conductivity of Na2FeSiO4 always limits its electrochemical reactivities and no effective solution has been found to date. Herein, the novel Ni-substituted Na2Fe1-xNixSiO4@C nanospheres (50-100 nm) encapsulated with a 3D hierarchical porous skeleton (named as alveolation-like configuration) constructed using in situ carbon are first synthesized via a facile sol-gel method, and the effects of Ni substitution combined with the design of a unique carbon network on Na-storage properties are assessed systematically, focusing on alleviating the inherent defects of the Na2FeSiO4 cathode material. A series of characterization technologies such as X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and so forth, coupled with the electrochemical measurements and first-principles calculations, are used to explore the structure, morphology and electrochemical behaviors of the as-prepared materials. The results show that the synergism between Ni substitution and the special alveolation-like configuration enables fast Na ions mobility (from 10-14 to 10-12 cm2 s-1), reduces band gap energy (from 2.82 to 1.79 eV) and lowers Na-ion diffusion barriers, finally reciprocating the vigorous electrochemical kinetics of the electrode. Especially, the elaborately designed material-Na2Fe0.97Ni0.03SiO4@C-displays superior Na-storage properties of around 197.51 mA h g-1 (corresponding to 1.43 Na+ intercalation) at 0.1 C within 1.5-4.5 V along with desirable capacity retention (84.44% after 100 cycles), and the rate capability is also markedly enhanced (a capacity of 133.62 mA h g-1 at 2 C). Such the effective methodology employed in this work opens a potential pathway to synthesize the silicate cathode material with excellent electrochemical properties.