A scalable inverse-microemulsion-polymerization-phase-separation coupling method is applied to successfully prepare hierarchical macropore-rich activated carbon microspheres (ACS) using a phenolic resin (PR) precursor followed by carbonization and KOH activation for the first time. The formed ACS materials are assembled by carbon nanoparticles (CNPs). The macropores interspersed among the component CNPs are formed after removing the non-reactive solvent phase in the course of the polymerization of the reactive PR phase, which occupies ∼64% of the total pore volume (∼2.779 cm3 g−1) of the optimized ACS. In combination with mesopores (∼18% of the total pore volume), the ACS possesses meso/macropores approaching 82% of the total pore volume. Micropores are created in the component CNPs via KOH activation, showing shortened ion transport distances in the nanoscale dimension. Both the hierarchical micro/meso/macroporous structure and the inner nanoparticle morphology (short ion diffusion pathways) can significantly contribute to the rapid transport of electrolyte ions throughout the carbonaceous matrix, resulting in superior rate performance of ACS-based supercapacitors. More importantly, the energy densities of the ACS supercapacitors operating in both aqueous and organic electrolyte retain steady over a wide range of power densities varying dramatically from 0.25 to 14.5 kW kg−1 and to 7.0 kW kg−1, respectively.