In this work we synthesized two novel isostructural twin hybrids Compl: [H-(C10H10N2)Cu-2][PMo12O40] & Comp2: [H(C10H10N2)Cu-2][PW12O40], based on the Keggin ions (PMo12O40-3 & PW12O40-3), Cu(I) cation, and 4,4'-bipyridine, by in situ hydrothermal reduction of Cu, facilitated through extensive standardizations of synthetic pH conditions. Both compounds crystallized in monoclinic P2(1)/c space group with similar lattice parameters and crystal structures. The structural similarity prompted us to explore comparative catalytic properties of the hybrids, to understand the relative role of the POM species in the activity. While characterization techniques like powder Xray diffraction (XRD), single-crystal XRD, IR, adsorption studies, etc. confirmed the identical structural hierarchy in the twin polyoxometalate-based metal organic frameworks (POMOFs), critical analyses through Xray photoelectron spectroscopy, X-ray absorption near-edge structure spectroscopy, and magnetic property studies elucidated the electronic and local structural properties of the two. The hybrids were highly active for heterogeneous catalysis of small-molecule oxidation, with Comp 2 showing better activity than Compl, particularly for oxidation of ethylbenzene and cyclooctene. Comp2 also outperformed Compl in photocatalytic degradation of methylene blue, with higher conversion efficiency of 83% and one order higher apparent rate constant of 0.0139 min(-1), which is comparable to that of the well-known photocatalyst, P25. Electrochemical pseudocapacitance studies revealed that these POMOFs are having the potential to act as good charge storage and conducting devices if their electrochemical stability can be improved.