Hierarchically porous carbon materials with interconnected frameworks of macro- A nd mesopores are desirable for electrochemical applications in biosensors, electrocatalysis, and supercapacitors. In this study, we report a facile synthetic route to fabricate hierarchically porous carbon materials by controlled macro- A nd mesophase separation of a mixture of polystyrene-block-poly(ethylene) and dopamine. The morphology of mesopores is tailored by controlling the coassembly of PS-b-PEO and dopamine in the acidic tetrahydrofuran-water cosolvent. HCl addition plays a critical role via enhancing the charge-dipole interactions between PEO and dopamine and suppressing the clustering and chemical reactions of dopamine in solution. As a result, subsequent drying can produce interpenetrated PS-b-PEO/DA mixtures without forming dopamine microsized crystallites. Dopamine oxidative polymerization induced by solvent annealing in NH4OH vapor enables the formation of percolating macropores. Subsequent pyrolysis to selectively remove the PS-b-PEO template from the complex can produce hierarchically porous carbon materials with interconnected frameworks of macro- A nd mesopores when pyrolysis is implemented at a low temperature or when DA is a minor component.