Herein, we present a facile synthesis of hierarchical carbon frameworks with microporous skeletons and interconnected meso/macropores by employing poly(vinylidene chloride-co-methyl acrylate)-b-polystyrene copolymers as precursors. The obtained porosity can be tuned over a broad range via well-selected block proportions of the precursor, enabling its advantageous applications in target-oriented energy storage systems.