Tuning the structural architecture of the pristine two dimensional hexagonal boron nitride (h-BN) nanosheets through rational surface engineering have proven advantageous in the fabrication of competent catalytic materials. Inspired by the performance of h-BN based nanomaterials in expediting key organic transformations, we channelized our research efforts towards engineering the inherent surface properties of the exclusively stacked h-BN nanosheets through the incorporation of a novel competent copper complex of a bidentate chelating ligand 2-hydroxy-4-methoxybenzophenone (BP). Delightfully, this hybrid nanomaterial worked exceptionally well in boosting the [3 + 2] cycloaddition reaction of azide and nitriles, providing a facile access to a diverse variety of highly bioactive tetrazole motifs. A deep insight into the morphology of the covalently crafted h-BN signified the structural integrity of the exfoliated h-BN@OH nanosheets that exhibited lamellar like structures possessing smooth edges and flat surface. This interesting morphology could also be envisioned to augment the catalysis by allowing the desired surface area for the reactants and thus tailoring their activity. The work paves the way towards rational design of h-BN based nanomaterials and adjusting their catalytic potential by the use of suitable complexes for promoting sustainable catalysis, especially in view of the fact that till date only a very few h-BN nanosheets based catalysts have been devised.