Two neutral and four-coordinate vanadium(V)-nitrido complexes have been prepared via the thermolysis of metastable vanadium(III)-azido precursors. All complexes have been fully characterized by multinuclear NMR, FT-IR, isotopic labeling, and, in most instances, single crystal X-ray diffraction. On the basis of activation parameters, N-2 extrusion to form the V N moiety is proposed to occur via an ordered and early transition state having three- or four-triazametallacycle frameworks. In addition, we demonstrate the nitrido ligand to undergo incomplete N-atom transfer to CO and CN {2,6-Me-2-C6H3} to form the bent V-N=C=X (X = O, N{2,6-Me-2-C6H3}) ligands with concomitant 2e(-) reduction at the vanadium center.