Three-dimensional beehive-like hierarchical porous carbons (HPCs) have been prepared by a facile carbonization of polymethylmethacrylate (PMMA)/polyacrylonitrile (PAN) core-shell polymer particle followed by KOH activation. The all-organic porogenic core-shell precursor was synthesized by a simple and green surfactant-free emulsion polymerization. The as-obtained HPCs show favorable features for electrochemical energy storage such as high specific surface area of up to 2085 m(2) g(-1), high volume of pores up to 1.89 cm(3) g(-1), hierarchical porosity consisting of micro, meso, and macropores, turbostratic carbon structure, uniform pore size and rich oxygen-doping (21.20%). The supercapacitor performance of HPCs exhibit a high specific capacitance 314 F g(-1) at a current density of 0.5 A g(-1) and 237 F g(-1) at a current density of 20 A g(-1), ultra-high rate capability with 83% retention rate from 1 to 20 A g(-1) and outstanding cycling stability with 96% capacitance retention after 2000 cycles. The facile, efficient and green synthesis strategy for novel HPCs from polymer sources could find use in supercapacitors, lithium ion batteries, fuel cells and sorbents. (C) 2016 Elsevier B.V. All rights reserved.