Vanadium oxides exhibit promising characteristics for electrochemical energy storage, owing to their capability to switch between different oxidation states, in combination with the incorporation of alkali metals. Here, we report on a systematic investigation of the mechanochemical reduction of V2O5 with NaH. In contrast to conventional high-temperature synthesis methods, the mechanochemical reaction occurs already after a few minutes. We observed a mixture of different (sodium) vanadium oxides with vanadium oxidation states ranging from +III to +V. Remarkably, these highly exothermic self-propagating reactions occur even within a rudimentary pistil-mortar setup. Hereby, the hydride concentration has a greater effect on the final sample composition than the milling time. In general, higher percentages of sodium vanadates are formed instead of vanadium oxides, and the lower oxidation states of vanadium are accessible with increasing amounts of NaH. Theoretical calculations confirm these experimental observations and emphasize the central role of sodium vanadates, especially with vanadium in the +V oxidation state, in carrying out the observed exothermic reactions. This comprehensive study sheds light on the mechanochemical reduction of vanadium oxides and underlines their potential for further development of electrochemical energy storage systems.