The sluggish kinetics of oxygen reduction reaction (ORR) hinders the commercialization of Zn-air batteries (ZABs). Manipulating the electronic structure of electrocatalysts to optimize the adsorption energy of oxygen-containing intermediates during the 4e− ORR offers a practical route toward improving ORR kinetics. Herein, we designed a novel ORR electrocatalyst containing Co single atoms and nanoparticles supported by carbon dots-derived carbon nanoflowers (Co SAs/NPs CNF). Co SAs/NPs CNF possessed a very high ORR activity (E1/2 of the Co SAs/NPs CNF catalyst is 0.83 V (vs. RHE)), and outstanding catalytic performance and stability when used as the air-electrode catalyst in rechargeable ZABs (152.32 mW cm−2, 1000.58 mWh gZn−1, and over 1300 cycles at a current density of 5 mA cm−2). The Co SAs and Co NPs cooperated to improve electron and proton transfer processes during ORR. Theoretical calculations revealed that the presence of adjacent Co NPs optimized the electronic structure of the isolated Co-N4 sites, significantly lowering the energy barriers for the rate-determining step in ORR (adsorption of *OOH) and thereby delivering outstanding ORR performance. This work reveals that the combination of supported single-atom sites and metal nanoparticles can be highly beneficial for ORR electrocatalysis, outperforming catalysts containing only Co SAs or Co NPs.