From first principles calculations, we show that (InN)32 nanoparticles favor rock salt structure compared with wurtzite structure in bulk. A phase transition from wurtzite to rock salt structure is known to occur in bulk InN at 12.1 GPa and higher values of pressure for AlN and GaN. However, at the nanoscale we show that this structural transition takes place in (InN)32 without applying pressure. The charge asymmetry value g and cationanion size ratio in InN describe very well this behavior. Similar studies on nanoparticles of AlN and GaN as well as a few other binary compounds such as MgS, AgI, ZnO, and CdSe, however, do not show such a transition. Our results suggest (InN)32 to be a unique candidate as further calculations on a few larger size (InN)n nanoparticles show that a filled cage (two shells) (InN)12at(InN)48 structure of (InN)60 has higher binding energy compared with a rock salt structure of (InN) 64 leading to the conclusion that other 3D structures are likely to become favorable over rock salt structure for larger sizes. © 2013 American Institute of Physics.