A robust paddle-wheel Cu(II)-based metal-organic framework (MOF) 1, having dual functionalities, namely, Lewis acid and basic sites, has been explored as a heterogeneous catalyst. This MOF, because of its large void volume (10298 angstrom(3), 67.6%), large surface area (1480 m(2)/g), and high thermal stability, encouraged us to see its applicability in two catalytic reactions, namely, oxidative C-O coupling (cross-dehydrogentaive coupling reaction) involving direct C-H activation and Friedlander reaction under solvent free and ambient conditions. This study demonstrates the green aspect of MOFs in coupling reactions because of the simplified recovery, shorter reaction time, minimum waste, and smooth activation of the C-H bond, which is very challenging in synthetic chemistry.