Bimetallic cooperative catalysts are of interest for the electrooxidation of organic molecules into valuable chemicals due to their enhanced activity and selectivity over monometallic materials. However, their mechanisms and design principles remain debated. This study introduces a Ni-Mn cooperative center for benzyl alcohol oxidation reaction (BOR), identified through theoretical screening of Ni-based bimetallic materials. A Ni-Mn catalytic layer was fabricated on nickel nanorod arrays, featuring amorphous MnPx on crystallized Ni2P (MnPx/ Ni2P NRAs). The MnPx/Ni2P NRAs electrode achieved a Faraday efficiency of 94.5 % for benzoic acid conversion. Mechanistic analysis revealed mutual activation between Mn dopants and the Ni matrix, forming active Mn-NiOOH sites at lower anodic potentials through surface electro-oxidative reconstruction. These Mn-NiOOH interfaces enhanced the adsorption of Ph-CH2O- * intermediates and accelerated their coupling with OH*, resulting in faster charge transfer kinetics and a lower energy barrier for BOR.