The synthesis and X-ray crystal structure of the first structurally characterized vanadium (V) complex containing a vanadium (V)-N-amide bond is reported. The square pyramidal geometry about the central ion contains an oxo, two alkoxide oxygen, and two deprotonated amide nitrogen donor atoms. The vanadium (V) oxidation state is confirmed by the presence of well-resolved H-1 and V-51 NMR signals as well as the absence of an ESR signal.