A flexible, 2-fold interpenetrated 3D supramolecular structure [Cu(ndc^2-)(1,10-phen)]_n (where ndc^2- = 2,6-napthalenedicarboxylate and 1,10-phen = 1,10-phenanthroline) comprising neutral 2D metal-organic layers as the basic building block was prepared. Structural study reveals that metal ions are bridged by ndc^2- ligands to form 2D coordination layers and the coordinated 1,10-phen moieties are hanging from the layers in the interalamellar spaces. The gliding motion of π···π stacked layers through 1,10-phen moieties was found to be responsible for the flexibility of MOF and the consequent extended conjugation also rendered semi-conducting behaviour in the material. Thermal stability studies revealed that the framework was pretty stable below 260°C. Additionally, the MOF was characterized by performing adsorption and photoluminescence studies. Further, the MOF was calcined at 650°C to prepare well defined, nearly uniform and spherical shaped CuO nanoparticles (CuO-NPs) with an average size of ~25 nm. Interestingly, CuO-NPs showed around 16 times more conductivity (4.8 x 10^-2 S/cm) in relative to the parent MOF (3 x 10^-3 S/cm). CuONPs induced cross-coupling reactions of alcohols and thiols with arylhalides have been reported. A simple, general, ligand-free and solvent-free procedure for the efficient synthesis of the cross-coupled products in high yield was successfully demonstrated.