The reactions of O(D-1) atoms with VF5 at room temperature have been studied by time-resolved laser magnetic resonance at the buffer gas (SF6) pressure of 6 Torr. The O(D-1) atoms were produced by the photodissociation of ozone using an excimer laser (KrF, 248 nm). By monitoring the kinetics of FO radical formation, the bimolecular rate constant of O(D-1) consumption in collisions with VF5 has been determined to be k(VF5) = (7.5 +/- 2.2) x 10(-11) cm(3) s(-1). The branching ratio for the channel producing FO radicals (k(8a)) has been found to be k(8a)/k(VF5) = 0.11 +/- 0.02. Quantum chemical calculations at the CCSD(T)/CBS level of theory give evidence that the reactions of O(D-1) with VF5 proceed via the VF4OF intermediate. The enthalpy of the reaction leading to this intermediate formation was calculated to be -245.8 kJ/mol. In qualitative agreement with the experimental results, the reaction channel O(D-1) + VF5 -> FO + VF4 (8a) turned out to be 72.9 kJ/mol energetically more favorable than the channel O(D-1) + VF5 -> F + OVF4 (8b). The dissociation enthalpy of the OVF4 radical was calculated to be very low (18.1 kJ/mol); hence, the decay of OVF4 to F + OVF3 should proceed very fast. The molecular channel O(D-1) + VF5 -> F-2 + VF3O, though being most favorable thermodynamically, is kinetically unimportant.