The Sabatier principle is widely explored in heterogeneous catalysis, graphically depicted in volcano plots. The most desirable activity is located at the peak of the volcano, and further advances in activity past this optimum are possible by designing a catalyst that circumvents the limitation entailed by the Sabatier principle. Herein, by density functional theory calculations, we discovered an unusual Sabatier principle on high entropy alloy (HEA) surface, distinguishing the “just right” (ΔG_H* = 0 eV) in the Sabatier principle of hydrogen evolution reaction (HER). A new descriptor was proposed to design HEA catalysts for HER. As a proof-of-concept, the synthesized PtFeCoNiCu HEA catalyst endows a high catalytic performance for HER with an overpotential of 10.8 mV at −10 mA cm⁻²and 4.6 times higher intrinsic activity over the state-of-the-art Pt/C. Moreover, the unusual Sabatier principle on HEA catalysts can be extended to other catalytic reactions.

SACs, DACs, and TACs, heterogeneous catalysts with the advantages of homogeneous catalysts, are ideal models for exploring catalytic mechanisms and further designing catalysts.

Potassium‐ion batteries (PIBs) are considered as promising candidates for lithium‐ion batteries due to the abundant reserve and lower cost of K resources. However, K⁺ exhibits a larger radius than that of Li⁺, which may impede the intercalation of K⁺ into the electrode, thus resulting in poor cycling stability of PIBs. Here, an N/O dual‐doped hard carbon (NOHC) is constructed by carbonizing the renewable piths of sorghum stalks. As a PIB anode, NOHC presents a high reversible capacity (304.6 mAh g⁻¹ at 0.1 A g⁻¹ after 100 cycles) and superior cycling stability (189.5 mAh g⁻¹ at 1 A g⁻¹ after 5000 cycles). The impressive electrochemical performances can be ascribed to the super‐stable porous structure, expanded interlayer space, and N/O dual‐doping. More importantly, the NOHC can be prepared in large scale in a concise way, showing great potential for commercialization applications. This work may impel the development of low‐cost and sustainable carbon‐based materials for PIBs and other advanced energy storage devices.