Electrochemical oxygen reduction reaction (ORR) is fundamental for many energy conversion and storage devices. Selective tuning of *OOH/*OH adsorption energy to break the intrinsic scaling limitation (ΔG_*OOH=ΔG_*OH+3.2 eV) is effective in optimizing the ORR limiting potential (U_L), which is practically challenging to achieve by constructing a particular catalyst. Herein, using first-principles calculations, we elucidated how to rationally plant an additional *OH that can selectively interact with the ORR intermediate of *OOH via hydrogen bonding, while not affecting the *OH intermediate. Guided by the design principle, we successfully tailored a series of novel carbon-based catalysts, with merits of low-cost, long-lasting, synthesis feasibility, exhibiting a high U_L (1.06 V). Our proposed strategy comes up with a new linear scaling relationship of ΔG_*OOH=ΔG_*OH+2.84 eV. This approach offers a great possibility for the rational design of efficient catalysts for ORR and other chemical reactions.