Porous carbon bricks have been synthesized by carbonizing self-assembled polymer bricks of poly(divinylbenzene-co-4-vinylbenzyl acetate) (P(DVB/VBA)). The synthesis process consists of (a) the preparation of colloidal polymeric nanoparticles by miniemulsion polymerization, (b) the self-assembly of such polymeric nanoparticles into brick-like aggregates by evaporation, and (c) carbonization. The resulting carbon bricks (denoted as SC, standing for carbons prepared from self-assembled polymer bricks) have hierarchical porous structures with a high specific surface area of 616 m(2) g(-1) and an average pore size of 5.2 nm. KOH activation of SC endows the ASC (activated SC) with an ultrahigh specific surface area of 2385 m(2) g(-1) and an average pore size of 2.7 nm. Both SC- and ASC-based electrodes as supercapacitors exhibit superior capacitance performance (207 F g(-1) for SC and 319 F g(-1) for ASC at a current density of 0.5 A g(-1)), good rate capacitive behavior and excellent cycling stability. Such performances highlight the potential of SC and ASC as electrode materials for widespread supercapacitor applications. (C) 2014 Elsevier Ltd. All rights reserved.