Mechanical milled powders of boron nitride were obtained. The microstructural characterization of these milled powders was carried out using X-ray diffraction technique. Insights on the nature of the crystalline phases obtained in these milled powders were obtained between comparisons of theoretical and experimental X-ray diffraction patterns. Observations on the phase transformations have been carried out using calorimetry and thermogravity experiments. Morphological and microstructural characteristics of nanocrystals are obtained using SEM and HRTEM instruments.