The transitions originating from triply excited, doubly autoionizing states of Li-like V formed in beam-foil experiments detected within a set of blended spectroscopic profiles have been assigned tentatively by the Hartree–Fock calculations including relativistic corrections and multi-configuration interactions as perturbations. The x-ray decay channels from the triply excited states such as 3p^{3 4}S, 2p²np⁴S (n ∼12) through radiative transitions to the ground state via two or more steps have been observed.