[PMo12O40(VO)(2)](5-) is a highly reduced cluster with eight d metal electrons. The localization-delocalization nature of d metal electrons is one of the points of interest in reduced polyoxoanions. We report DFT calculations which suggest that the oxidation state of the V atoms is +4 and that the other six metal electrons are delocalized between the 12 Mo atoms. The calculations also provide evidence that the anion [PMo12O40(VO)(2)](5-) should be paramagnetic.