The development of green and clean synthetic techniques to produce carbon materials for energy storage and conversion applications has motivated researchers to use sustainable biomass. In this study, hierarchical porous carbon (HPC) with very high specific surface area and controlled porosity is synthesized by a novel and facile method, which employs an exothermic pyrolysis process of starch−magnesium nitrate raw materials with subsequent high temperature thermal treatment and acid washing. The biomass starch acts as both a reductant and carbon source, while magnesium nitrate is an oxidant and provides MgO template as pore creator. The vigorous exothermic pyrolysis of starch−magnesium nitrate mixture introduces MgO@C precursor with a highly 3D porous network containing meso-and macropores. After MgO template is removed, plenty of micro-and mesopores are further created. Experimental parameters including calcination temperature, starch−nitrate ratio, and magnesium salt species are comprehensively evaluated. The HPC shows a very large specific surface area up to about 2300 m 2 g −1 and a hierarchical porous architecture composed of interconnected micro-, meso-and macropores. As an electrode material for supercapacitors, the HPC exhibits high specific capacitance (229 F g −1 at 1 A g −1 in a 6 M KOH electrolyte), good rate capability (211 F g −1 at even 10 A g −1 ) and outstanding cycling stability (94% capacitance retention after 10 000 cycles at 2 A g −1 ). The superior electrochemical performance of the HPC stems from both high surface area and the hierarchical multiporous structure, which provides an accessible pathway for electrolyte transport. These results demonstrate a very effective and low-cost method for scalable preparation of HPC using green biomass carbon source for supercapacitors, which also has potential applications such as adsorbent for water/gas treatment.