Two electron-rich, metal-metal bonded pentamolybdate hybrids, 2D-[MoIV3MoVI2O 10 Sr 2 (H 2 O) 5 (C 6 H 4 O 7 ) 2 py 3 ]·3.5H 2 O (1) and 1D-[MoIV3MoVI2O 10 Sr(H 2 O) 3 (C 6 H 4 O 7 ) 2 py 3 ]·py·2[NH 2 (CH 3 ) 2 ]·2H 2 O (2, py = pyridine), were prepared by the partial solvothermal oxidation of [MoIV3O 2 (O 2 CCH 3 ) 6 (H 2 O) 3 ]ZnCl 4 ·8H 2 O and citric acid in py/H 2 O (for 1) or py/H 2 O/DMF (for 2). Both 1 and 2 feature a triangularly metal-metal bonded incomplete cuboidal [MoIV3O 4 ] unit. Redox-active 6 e -[MoIV3O 4 ] units can serve as an "electron sponge" to store/release six electrons reversibly via Δ-bond breakage and re-formation during charging/discharging processes. 1 and 2 further form 3D and 2D supramolecular structures, respectively, through slipped π-π stacking interactions between the pyridine ligands. Both the incorporated 6 e -redox active [MoIV3O 4 ] unit and the 3D/2D supramolecular conductive networks in hybrid-POM 1/2 remarkably enhance the electronic conductivity and reversible multi-electron redox ability with the structural integrity retained. Consequently, 1 and 2 exhibited high discharge specific capacities of 236.0 and 277.0 mA h g -1 at 50 mA g -1 , respectively, and a good cycling performance at high current density (121.8 mA h g -1 , 2 A g -1 for 2), providing a new way for improving POM-based electrode materials.