This highly reactive species is noteworthy from theoretical perspectives as a rare isolable homoleptic metal carbonyl that is paramagnetic.

Most species with the formula Mx(CO)y follow the 18-electron rule, whereas V(CO)6 has 17 valence electrons.

This triether solubilizes sodium salts, akin to the behavior of a crown ether: The resulting anion is oxidized with acid:[2] Vanadium hexacarbonyl is thermally unstable.

V(CO)6 reacts with sources of the cyclopentadienyl anion to give the orange four-legged piano stool complex (C5H5)V(CO)4 (m.p. 136 °C).

V(CO)6 adopts an octahedral coordination geometry and is isostructural with chromium hexacarbonyl, even though they have differing valence electron counts.