Lithium-ion battery (LIB) is a commercially successful energy storage system with superior energy and power densities. Cathodes used in a LIB significantly decide its performance; however, cheaper and high voltage cathodes are essential. Among the cathode materials, vanadium-based polyanionic compounds are attractive due to their high voltage and abundance. In this talk, I will present the results and highlight the outcome from the studies on LiVPO4F, Li3V2(PO4)3, and phase stability of Li2VP2O7. LiVPO4F requires optimization in the synthesis to retain the stoichiometric composition devoid of other secondary phases. This has been achieved by a combined sol-gel and solid-state reaction with optimum PTFE content. Further, optimizing the carbon coating and the role of this on the electrochemical properties are studied. Best electrochemical performances, mainly attributed to the optimized PTFE to precursor mass ratio used during synthesis and phase pure LiVPO4F produced with an optimum addition of oleic acid and lauric acid with discharge capacities of 96.3 mAh/g (44.6 mAh/g) at 0.1C (10C)-rate will be highlighted. The microstructures also play an important role in bettering the electrochemical properties. This has been demonstrated on another promising vanadium-based cathode, Li3V2(PO4)3, prepared with carbon (C) coatings in both nanoparticulate (LVP/C-np) and nanofibrous (LVP/C-nf) forms using a sol-gel and electrospinning processes, respectively. LVP/C-np and LVP/C-nf cathodes exhibited a discharge capacity of 137 mAh/g and 124 mAh/g at 0.1 C rate (cycling voltage range 3 V to 4.8 V). Electrochemical studies show that the nanofibrous cathodes have better rate capability with a capacity of 58.74(28.75) mAh/g even at 10C(30C)-rate compared to nanoparticle cathodes (37.23 mAh/g at 10C-rate), indicating that one-dimensional structure improves the high-rate capability performance of cathodes. LiVP2O7 is a well-explored cathode that supports single electron extraction with a capacity of 115 mAh/g. With the addition of Li and F, it should be possible to extract two moles of lithium from the hypothetical Li2VP2O7F system. Multi-electron reaction materials Li2VP2O7F are attempted to explore this possibility. However, several syntheses made with final annealing in the Ar and N2/H2 with and without F resulted in identical XRD patterns similar to the one reported in the literature. We find that it is neither Li2VP2O7F nor Li2VP2O7; instead, it is a structural mixture of three different phases viz., Li9V3(P2O7)3(PO4)2, Li3V2(PO4)3, and LiVP2O7, as discerned from the detailed structural studies performed using X-Ray diffraction and Rietveld refinement. The electrochemical properties, in fact, show two Li extraction showing promising futuristic cathodes with high capacity (> 300 mAh/g).