In this study, we developed a facile and template-free strategy for the preparation of activated porous carbon beads (APCBs) from polyacrylonitrile. The chemical activation with KOH was found to enhance the pore properties, such as specific surface area (SSA), pore volume, and pore area. The APCBs exhibited a large SSA of 1147.99 m2/g and a pore area of 131.73 m2/g. The APCB-based electrodes showed a good specific capacitance of 112 F/g at 1 A/g in a 6 M KOH electrolyte, and excellent capacitance retention of 100% at a current density of 5 A/g after 1000 cycles. Therefore, the APCBs prepared in this study can be applied as electrode materials for electric double-layer capacitors.