Two groups of RF-sputtered BN films (pure hexagonal phase and approximately 27.5% cubic content, respectively) were annealed at 600 to 1000 degrees C under nitrogen at atmospheric pressure after deposition. FTIR spectroscopy indicates a reversible transformation from hexagonal phase to cubic phase, and again hexagonal phase. The most effective temperature for h-BN converting to cubic zincblende (c-BN) is 900 degrees C. Further, the indirectly stepwise transformation from hexagonal (h-BN) to explosive BN (E-BN) and then to c-BN employing metastable E-BN as an intermedium was observed. In addition, we tentatively put forward that the existence of defective h-BN and the N defects plays a key role on h-BN to c-BN transformation. (C) 2008 Elsevier B. V. All rights reserved.