Active oxygen radicals (OH*/O*/OOH*) generated from oxygen evolution reaction (OER) play a crucial role in facilitating the electrooxidation of organic compounds into high value-added chemicals. However, constructing atomically precise active sites with a specific function to catalyze water-coupled electrooxidation reactions in a tandem system still confronts a great challenge. Herein, we propose a novel water-participating benzyl alcohol electrooxidation tandem process by constructing homogeneous isolated Fe–Pt dual-atom site catalysts on CoOOH nanosheet arrays (FePt DAC). The Fe and Pt dual atomic sites synergistically deliver excellent benzyl alcohol oxidation reaction activity with a high current density of 1500 mA·cm⁻² at a low potential of 1.49 V (vs. reversible hydrogen electrode (RHE)) and remarkable long-term durability without obvious attenuation after 530 h operation. In-situ Fourier-transform infrared spectroscopy, isotopic tracing experiment, and detailed theoretical calculations further reveal the tandem mechanism, in which the in-situ generated O* species on the Fe site through OER process serve as key intermediates that bridge the subsequent electrochemical benzyl alcohol oxidation on neighboring Pt site. This coupled oxidation mechanism turns competitive OER process into mutual benefits and provides insights to achieve directional transformation of chemical bonds via construction of collaborative dual atomic sites.