A series of dinuclear organophosphorus-bridged complexes of the general formula {(LVO(mu-O2PRR')}(2) [L = eta(5)-cyclopentadienyltris(diethylphosphito-kappa P-1) cobaltate(III)] has been synthesized as a structural model for the industrially used vanadium phosphate oxidation catalysts. These dimeric species contain two vanadium centers in a VO6 environment bridged by O-P-O units. These complexes have been characterized via spectral and magnetic analyses. Structural parameters have been analyzed through X-ray diffraction. The dimers generally exist in either a cis/cis-anti or retracted chair conformation in the solid state. The syntheses, structural, spectral, and magnetic data are presented and discussed here.