The excited state dynamics of a d0 vanadium(V) oxido ligand-to-metal charge transfer (LMCT) complex, VOLF, were investigated via a combination of static optical and X-ray absorption (XAS) spectroscopy, transient optical absorption spectroscopy, and time-dependent density functional theory (TD-DFT). Upon excitation of the LMCT in the visible region, transient absorption data reveal that internal conversion traps the excited carrier population into a long-lived charge transfer state of 3dxy electron character, S1(dxy). The internal conversion is substantiated by an isosbestic point in the transient absorption data, two nearby charge transfer states that couple well by TD-DFT, multiple rates in the ground state recovery, and the decay kinetics of an excited state absorption with the energy of a d-d transition in O K-edge XAS spectra. The long lifetime (∼420 ps) of S1(dxy) can be ascribed to its poor optical and vibrational coupling to a distorted ground state (S0*) via a negligible electronic dipole transition in TD-DFT. The lack of luminescence or an identifiable triplet state also suggests attributing the lifetime to electronic contributions. In conjunction with its strong visible absorption and reduction potential, the long-lived LMCT suggests that molecules such as VOLF could have potential utility for energy conversion applications. Moreover, the results show that internal conversion between two nearby charge transfer states, differentiated by their 3d character, can form a long-lived charge transfer excitation, broadly informing the discovery of 3d metal-centered optical absorbers with long-lived charge transfer lifetimes.