Hexagonal boron nitride (hBN) nanowalls were deposited by unbalanced radio frequency sputtering system on (100)-oriented silicon, nanocrystalline diamond films, and amorphous silicon nitride (Si 3 N 4 ) membranes. The hBN nanowall structures were found to grow vertically with respect to the surface of all of the substrates. To provide further insight into the nucleation phase and possible lattice distortion of the deposited films, the structural properties of the different interfaces were characterized by transmission electron microscopy.Hexagonal boron nitride (hBN) has a structure similar to graphite, in which B and N atoms are bound alternatively in in-plane hexagonal rings forming two dimensional (2D) sheets, which are held together by van der Waals forces, forming the hBN lattice. hBN can be synthesized into nanostructured films, such as nanowalls, with tunable properties depending on the growth parameters, to make it insulating, highly compressible, or to improve its lubricity [1,5]. Grown hBN structures have so far shown a considerable number of defects and disordered BN phases, i.e. amorphous and turbostratic boron nitride (aBN and tBN), particularly at the initial stages of thin film growth. The presence of those phases is largely dependent on dynamics of chemical reactions at the substrate surface [1]. A substrate material that reduces these defective phases, creating a direct interface to the hBN phase, is therefore highly desirable.Many excellent properties of diamond, such as a negative electron affinity on hydrogen terminated surfaces, mechanical hardness, chemical inertness, and good thermal conductivity