[en] Highlights: • Reduced graphene oxide@boron nitride nanosheet (RGO@BNNS) hybrids are prepared. • The hybrids are fabricated for the first time by template-assisted autoclave pyrolysis technique at the temperature as low as 600 °C. • BNNSs on the surface of RGO can serve as high-performance oxidation-resistant coatings at high temperatures. • The hybrids can sustain up to 800 °C over a relatively long period of time. • The developed method can be scaled into gram-scale synthesis of the material. - Abstract: Reduced graphene oxide@boron nitride nanosheet (RGO@BNNS) hybrids were prepared for the first time using template-assisted autoclave pyrolysis technique at the temperature as low as 600 °C. The developed method can be scaled into gram-scale synthesis of the material. The BNNSs combine with RGO through van der Waals interplanar interaction without damaging the structures of RGO. Such ultrathin BNNSs on the surface of RGO can serve as high-performance oxidation-resistant coatings in oxidizing atmospheres at high temperatures. The RGO@BNNS hybrids can sustain up to 800 °C over a relatively long period of time.