In this work, the electronic structure and properties of NASICON-structured A4V2(PO4)3, where A = Li, Na, K were studied using hybrid density functional theory calculations. The symmetries were analyzed using a group theoretical approach, and the band structures were examined by the atom and orbital projected density of states analyses. Li4V2(PO4)3and Na4V2(PO4)3adopted monoclinic structures with theC2space group and averaged vanadium oxidation states of V+2.5in the ground state, whereas K4V2(PO4)3adopted a monoclinic structure with theC2space group and mixed vanadium oxidation states V+2/V+3in the ground state. The mixed oxidation state is the least stable state in Na4V2(PO4)3and Li4V2(PO4)3. Symmetry increases in Li4V2(PO4)3and Na4V2(PO4)3led to the appearance of a metallic state that was independent of the vanadium oxidation states (except for the averaged oxidation stateR32Na4V2(PO4)3). On the other hand, K4V2(PO4)3retained a small band gap in all studied configurations. These results might provide valuable guidance for crystallography and electronic structure investigations for this important class of materials.