The hydrothermal reaction of V2O5, V2O3, 2,2'-bpy and Na2SO4 in dilute sulfuric acid yields a novel hybrid, [VIVO(mu 3-SO4)(2,2'-bpy)]infinity, which demonstrates the potential of constructing a new class of robust composite solids composed of a (V/O/SO4)-based framework decorated with organic functionalities by combining appropriate vanadyl sulfate motifs with a variety of organic ligands.