Direct chemical vapor deposition (CVD) growth of single‐layer graphene on CVD‐grown hexagonal boron nitride (h‐BN) film can suggest a large‐scale and high‐quality graphene/h‐BN film hybrid structure with a defect‐free interface. This sequentially grown graphene/h‐BN film shows better electronic properties than that of graphene/SiO2 or graphene transferred on h‐BN film, and suggests a new promising template for graphene device fabrication.