A unique attempt to exploit silicate chemistry for a possible enhancement of the electrochemical properties of a lithium ion system via exploration of the novel category lithium intercalating LiNiSiO₄ cathode has been made through the present study. A novel citric acid assisted modified sol–gel method (CAM sol–gel) has been adopted to synthesize the title compound with a formation temperature positioned well below 500 °C, as derived from thermal studies. A powder x-ray diffraction (PXRD) pattern evidenced the absence of undesirable peaks and confirmed the formation of a hexagonal lattice structure with enhanced crystallinity and phase purity, and the presence of uniformly distributed particles of ~200 nm size with well defined grain boundaries is obvious from the scanning electron microscopy (SEM) image of LiNiSiO₄ material. Further, magic angle spinning (MAS) ⁷Li nuclear magnetic resonance (NMR) results from LiNiSiO₄ confirmed the presence of a layered type of crystal arrangement. A cyclic voltammetry (CV) study performed on a LiNiSiO₄ cathode revealed an excellent reversibility without any change in the peak position upon extended cycling, thus substantiating the structural stability upon progressive cycling.