A new complex containing the {OVv(mu-O)(VO)-O-v}(4+) unit has been synthesized and structurally characterized. Cyclic voltammogram of this complex showed that the two V-V centers of the V2O34+ core are found to undergo electrochemical reduction in two distinctly separate steps not observed previously in similar systems. A rare mixed-oxidation state species [L(O)(VOV)-O-IV(O)L](-) has been electrogenerated from the structurally characterized parent divanadium (V) species in solution state and characterized by IR, EPR, and electronic spectroscopy.