In this work, we have demonstrated the exfoliation of hBN sheets and used their surfactant-like properties to stabilize water-in-oil emulsions. The exfoliation was thermodynamically driven as the spreading hBN sheets separated the oil and water and lowered the system's free energy. Optical and TEM images showed the film of overlapping hBN sheets surrounding the dispersed aqueous phase, and using acoustic spectroscopy, we showed the diameter of the dispersed phase droplets to be a function of the size of the hBN flakes and the amount of hBN used. The effect of mixing time was also investigated, and it was found to be a significant parameter in polyHIPE morphology.