Heterostructures based on combining two-dimensional (2D) crystals in one stack have unusual physical properties and allow the creation of novel devices. Although this method of mechanically transferring individual 2D crystals is required for precise control, it is not scalable. Large-scale fabrication of heterostructures remains a key challenge for practical applications. Here, we provide a simple solution-based method using electrostatic interaction assembly of boron nitride (h-BN) and graphene to produce hybrid films with van der Waals heterostructures. The hybrid films prepared by this fabrication method tend to be alternately stacked and provide compact structured films. For a potential application, the h-BN/graphene hybrid films are fabricated supercapacitor’s electrodes revealing high volumetric capacitance, superior rate capability, a permanent life cycle, and high flexibility due to their synergistic effects. We anticipate that the hybrid films are useful as scalable flexible electrodes in supercapacitors, and our solution-based method has great potential for application in energy storage and electronics.