The compound Li X NiVO4 (X = 0.8, 1.0, 1.2) is prepared by a solid-state reaction method. The vibrational analysis of the compound is studied using Fourier transform infra red (FTIR) and Raman spectroscopic techniques. A new peak at 1039cm−1 is observed for Li1.2NiVO4 in the FTIR analysis and indicates the presence of Li+ OV bond interactions. The FTIR and Raman characteristic bands for cubic inverse spinel structure are observed for all samples. Using the diatomic approximation method, the bond length and the bond order of the compound with various Li compositions are calculated. The valence state of the compounds is calculated using the Pauling valence sum rule and is found to be nearly 5.2 for all compositions of Li X NiVO4 (X = 0.8, 1.0, 1.2).