Phosphatovanadium and phosphonatovanadium compounds known to date all have bridging phosph(on)-ato groups. The new diethyl phosphato compound (dipic)V(=O)(O2P(OEt)(2)) (2) has been prepared by removing the alcohol from mixtures of diethyl hydrogen phosphate and the alkoxy compound [(dipic)V(=O)((OPr)-Pr-i)](2) . xHO(i)Pr (1). Compound 2 is dimeric in the solid state with each diethyl phosphato group bridging two vanadium centers, but each diethyl phosphato group is strongly bonded to only one vanadyl center and is surprisingly easily displaced by reaction with alcohols.