Trimethyl vanadate(V), OV(OCH3)(3) (1), is examined by various mass spectrometric means. Photoionization experiments yield an ionization energy of IE(OV(OCH3)(3)) = 9.54 +/- 0.05 eV for the neutral molecule. The primary fragmentation of the molecular cation 1(+), i.e., loss of neutral formaldehyde, can occur via two independent routes of hydrogen migrations to afford the formal V-IV compounds HOV(OCH3)(2) and OV(OCH3)(CH3OH)(+), respectively. These two pathways are associated with low-lying activation barriers of almost identical height. At elevated energies, direct V-O bond cleavage of 1(+) allows for expulsion of a methoxy radical concomitant with the generation of the cationic fragment OV(OCH3)(2)(+), a formal V-V compound. Trimethyl vanadate can also form a molecular anion, 1(-), whose most abundant dissociation channel involves loss of a methyl radical, thereby leading to the formal Vv compound OV(OCH3)(2)O-. Various mass spectrometric experiments and extensive theoretical studies provide detailed insight into the ion structures and the relative energetics of the primary dissociation reactions of the molecular cations and anions of 1.