Boron nitride (BN) bears highly similar structures as carbon nanodiamond (ND) that are well-known as unique nanoparticle (NP) materials finding a myriad of useful applications, e.g., fluorescent biomarkers, electronics, photovoltaics, plasmonics, catalysis. Theoretical investigations on ND and BN NPs suggest the unique possibility of surface structural arrangements that affect core structures, and hence, result in possible large internal stresses in these nanostructures. Specifically, h-BN (Point group = D6h, Space group = P63/mmc) and c-BN (Space group = Fd3m) have generated tremendous scientific and technological interests due to their analogous structures and properties with graphite and diamond, respectively. The c-BN (lattice constant = 0.361nm) and diamond (0.356nm) exhibit strong interatomic potentials that lead to the highest hardness (∼7500 kg mm−2 for c-BN and ∼10,000 kg mm−2 for ND) and stiffness (Young’s modulus ∼700 GPa for c-BN and ∼1000 GPa for ND). Apart from that, c-BN exhibits high thermal conductivity (~12 W cm−1 K−1), close to that of diamond ~20 Wcm−1 K−1, which has one of the highest values including that of copper (~4 W cm−1 K−1), while the coefficient of friction for c-BN and ND is the lowest (less than 0.1) among all known materials. However, c-BN has certain advantages over ND, namely: 1) it is more oxidation-resistant; 2) it has higher thermal stability and hence, less reactive even at high temperatures with ferrous alloys; and 3) it is a wide-band-gap semiconductor (Eb~5.5 eV). Such properties make c-BN coatings the Holy Grail in materials science research for machining alloys, protective shells on energetic materials as well as for advanced semi-conductor materials. Specifically, the origin of unique surface nanostructures of BNNPs, when combined with the aforementioned diverse interfacial properties, can provide paradigm shift in the design of novel NPs with tunable interfacial stresses and activities – for both catalytic and next-generation energetic materials. But a fundamental knowledge gap exists in the rational design and synthesis of such metastable NPs due to the highly challenging and complex synthesis routes involved. We address the aforementioned knowledge gap through high-energy laser ablation-based rational design, and synthesis combined with structure-property characterizations of c-BN NPs (<10 nm sizes) comprising fullerene-like surface nanocage structures.