<p>The simple processing of graphene film electrodes with high mass loading provides enormous possibilities for customizing its hierarchical pore structure and characteristics for energy storage capabilities. Here, a hierarchical graphene film electrode was obtained via an effective strategy in which sodium camphor sulfonate (CAS) was used as a green pore-forming agent for modulating the porosity of the graphene film. The introduction of CAS can alleviated the issue of stacking of reduced graphene oxide (rGO) sheets, easily sublimed at relatively low temperatures for fine-tuning of pore characteristics. The optimized graphene film with increased micropores and mesopores provides high specific capacitance (150&#xa0;F g⁻¹ at 0.1&#xa0;A g⁻¹), rate capacity (100&#xa0;F g⁻¹ at 10&#xa0;A g⁻¹), capacity retention (98.1% over 10,000 cycles), and energy density (1.6&#xa0;mW h cm⁻² at 7.2&#xa0;mW cm⁻²). The prepared graphene film materials hold immense potential for constructing high-performance film electrodes for electrochemical energy storage.</p> Graphical Abstract <p></p>