Rational interface control of porous carbon electrode materials is of significance for achieving efficient supercapacitors. Herein, biomass-derived carbon microspheres with a highly graphitized porous surface and amorphous subsurface were well constructed via a flexible coupled catalysis-activation process. The unique structure not only endows the carbon microspheres with rapid electron transfer but also an ultra-high specific surface area. Owing to the optimized graphitized/amorphous structure, the obtained graphitized and activated starch-derived carbon microspheres display obviously impressive energy storage capability among the reported starch-derived carbon materials, even though they were evaluated in a narrow voltage window. The assembled symmetrical supercapacitor based on the optimized carbon microspheres exhibits a high capacitance of 198 F g⁻¹ at 1 A g⁻¹, a high energy density of 14.67 W h kg⁻¹ at a power density of 4142.80 W kg⁻¹, robust cycle performance, and good rate performance in alkaline aqueous electrolyte. This work provides a strategy for flexible construction of biomass-derived carbon electrode materials, with an optimized graphitized/amorphous and porous structure, for boosted energy storage in supercapacitor applications.