A detailed analysis of the electronic spectrum of the V 2+ Tutton's salt (NH 4) 2V(H 2O) 6(SO 4) 2 and its deuterate is presented. The spectra exhibit a number of unusual features including some not previously noted in earlier studies of this compound. In particular, there is structure superimposed on the 4A 2g→ 4T 2g band envelope ascribed to Fano antiresonances, which is due to the interaction of the 2E g and 2T 1g spin forbidden states with the 4T 2g state. The duplication of this structure in a much less intense band ∼ 3200 cm −1 to higher energy, suggests that the latter is induced by coupling of the 4T 2g state to an OH stretching frequency, and this is confirmed by deuteration. A similar band coupled to the 4T 1g(F) state is observed at ∼ 22000 cm −1. From the spectral assignments, angular overlap model ligand field parameters are obtained and the bonding in the [V(H 2O) 6] 2+ complex is discussed.