Porous starch was used as a precursor for hierarchical porous carbon microspheres. The preparation consisted of stabilisation, carbonisation and KOH activation, and the resultant hierarchical porous carbon microspheres had a large BET surface area of 3251 m(2) g(-1). Due to the large surface area and the hierarchical pore structure, electrodes made of the hierarchical porous carbon microsphere materials had high specific capacitances of 304 F g(-1) at a current density of 0.05 A g(-1) and 197 F g(-1) at a current density of 180 A g(-1) when used in a symmetric capacitor with 6 M KOH as the electrolyte. After 10,000 cycles, the capacitor still exhibited a stable performance with a capacitance retention of 98%. These results indicate that porous starch is an excellent precursor to prepare high performance electrode materials for EDLCs. (c) 2013 Elsevier Ltd. All rights reserved.