Graphene–boron nitride (BN) nanosheet heterostructures have become one of the highly interesting matters in recent times owing to their advantages. In this study, the liquid phase exfoliation method was preferred for production of graphene–BN nanosheet heterostructures. However, a pre-milling process was applied to starting materials, instead of the classical liquid phase exfoliation method previously used in the literature. Hexagonal graphite (h-G) and h-BN mixtures were milled for 50 h and the milled powders were subjected to the liquid phase exfoliation process. As a result of the examinations, it was observed that graphene–BN nanosheet heterostructures were successfully synthesized. The widths of the synthesized nanosheets were 300–500 nm and nanosheets were multi-layers. It was seen that a large part of the powder mixture were occurred at high amorphization during the ball milling process. According to X-ray diffraction (XRD) peaks, the amorphization ratio was almost 90%. But, almost all of amorphous structures were removed during acid mixing and the thermal process. But, amorphous structures still existed in samples. In addition, the ball milling process damaged the sheets and defects formed. Despite all these disadvantages, the milling process carried out in this study provided formation of thinner and larger sheets compared with previous similar studies.