In the designed synthesis, self-supported NH4V3O8 nanobelt arrays were prepared via a low-temperature solvothermal method. Then the NH4V3O8 nanobelt arrays were calcined in air atmosphere. Finally, a self-supported pattern of oriented V2O5 nanobelts was obtained for the first time. Further characterization methods certified that the growth direction of NH4V3O8 nanobelts was perpendicular to the orientation plane of self-formed NH4V3O8 sheet-like substrates. As a result, the nanobelts should stretch easily on the sheet-like substrate in an oriented manner. We prove that the solvent of ethanol plays a key role in the reaction and crystal growth process. It balances the two competing oxolation and olation reactions. Furthermore, the unique pattern served as high performance a lithium-ion battery and supercapacitor. Overall, the excellent electrochemical performances, for example, outstanding rate stability, remarkable cycling capacitance and ultrahigh capacity verify that the self-supported alignments have great potential applications in lithium-ion batteries and supercapacitors.