In our work, we used hBN to stabilize a water-in-oil emulsion and polymerize the continuous oil phase, forming a polymerized high internal phase emulsion (polyHIPE) containing a bicontinuous network of hBN. This approach allowed us to exploit the features of hBN without requiring hBN functionalization, thus maintaining cost-effectiveness and flame resistance at low concentrations of hBN. We introduce the exfoliation mechanism of hBN and the subsequent assembly of individual sheets. Additionally, we discuss the underlying mechanism of interfacial trapping with hBN and the surfactant-like characteristics of this two-dimensional material by focusing on the diameter of the emulsion droplets, the volume of emulsion phases, and the degree of sheet exfoliation. Additionally, the polymerization rate using water-insoluble BPO and watersoluble KPS was compared. Finally, the flame retardancy of the composite was studied using a Microscale Combustion Calorimeter.