Carbonaceous material is considered as the most promising anode material for potassium ion batteries (KIBs) in the advantages of low price, stable physical/chemical properties, and renewable resources. However, the moderate capacity and sluggish kinetics cast a shadow over its application. Here, we synthesize multiple active sites decorated porous hollow carbon nanospheres (S/N-PHCs) by a one-step large scalable carbonization method with polypyrrole coated polystyrene and low-cost sulfur as precursors. The obtained S/N-PHCs exhibits an amorphous nanocarbon structure with high specific surface area (502.2 m² g^-1) and S, N content of 9.12 and 3.14 at.%, respectively. The porous hollow nanospheres structure promotes the fully utilization of multiple active sites and a capacitive-dominated K⁺ storage. Consequently, the S/N-PHCs electrode delivers an ultrahigh specific capacity of 460.6 mAh g^-1 at a current density of 100 mA g^-1 with an initial Coulombic efficiency of 67.7% and excellent rate capability of 228.1 mAh g⁻¹ at 5000 mA g⁻¹. Moreover, a high reversible capacity of 249.7 mAh g^-1 can be retained over 1000 cycles at 1000 mA g⁻¹ (83.4% of the initial specific capacity), demonstrating a remarkable cycle stability. This work provides a scalable and environmentally friendly strategy to achieve hierarchical amorphous carbon as superior anode for KIBs.