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 LiNiSiO(4) 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 LiNiSiO(4) material. Further, magic angle spinning (MAS) (7)Li nuclear magnetic resonance (NMR) results from LiNiSiO(4) confirmed the presence of a layered type of crystal arrangement. A cyclic voltammetry (CV) study performed on a LiNiSiO(4) cathode revealed an excellent reversibility without any change in the peak position upon extended cycling, thus substantiating the structural stability upon progressive cycling.