In this work, the characterization of two hexagonal boron nitride (h-BN) samples has been carried out using several techniques, mainly XRD, SEM, TEM and Electron Diffraction. XPS was used for the analysis of powder surfaces. Despite the same synthesis procedure being used for both samples, there are differences between them. The two samples are highly crystalline according to the XRD results. The results suggest that there are minor impurities. Thus, XPS data have shown differences between the surface and bulk composition with presence of oxygen, associated with boric oxide. There are also differences in particle size between the samples, as deduced from electron microscopy and particle size measurements by laser scattering. This was also confirmed by pore volume variations after nitrogen adsorption measurements. The characterization of these materials is of primary importance in order to better understand the processing behaviour using these powders.