In this study, h-Boron Nitride (h-BN) nanosheets have been successfully exfoliated using Bougainvillea flower extract and ultrasonication process. The microstructural parameters such as microstrain, stress, and energy density were calculated using Williamson–Hall analysis. The time of ultrasonication and post-annealing temperature significantly alter the microstructure parameters such as crystal size, microstrain, stress, and energy density upon sonication. The lattice constants such as a-axis and c-axis, cell volume, and bond length did not alter significantly which confirms that there is no crystal structure deformation upon sonication and annealing processes. FESEM result revealed that exfoliation of h-BN and ultrasonication duration greatly influenced the exfoliation. Raman and FTIR studies confirm the pure phase of h-BN without secondary impurities. A simple ultrasonication process would effectively exfoliate h-BN layers and this could be used for tribological applications to reduce the friction between rubbing surfaces.