© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The reduction of V2O5 to vanadium metal(0), that requires severe conditions in conventional reduction methods, was enabled to be proceeded in a short time of 1 h at 1273 K by the reaction with magnesium vapor with the isolation yield of V(0) in 55.6% by using microwave irradiation of 820 W. A pressurized pelletization of powdery V2O5 well-mixed with MgO powder at a specific mixing ratio followed by calcination in ambient air at 1173 K was crucial for the reaction since a complex oxide of MgV2O4, presumably as a precursor, was formed in calcination of the V2O5/MgO pellet to be reduced to V(0) by the reaction with magnesium. Calcination of V2O5/MgO pellets with different mixing ratios or different temperatures resulted in the formation of different kinds of complex oxide of vanadium and magnesium such as α-Mg2V2O7, Mg3(VO4)2, triclinic Mg2V2O7, and MgV2O6. While the yield of V(0) was dependent on the kind of the complex oxide, formation of MgV2O4 was essential as the precursor to the formation of V(0).