Rhodium (Rh)‐based catalysts may solve the long‐standing inefficient oxidation of ethanol for direct ethanol fuel cells (DEFCs); however, the performance of ethanol oxidation reaction (EOR) on existing Rh‐based catalysts are far limited. Herein, the Rh–Pb catalysts are synthesized by building Pb and Pb oxide around Rh nanodomain, which shows highly efficient splitting CC bond and facile further oxidation of as‐generated C1 intermediates (COad and CHx fragments). It exhibits an ever‐highest EOR peak mass activity of ≈2636 mA mg−1Rh among Rh‐based catalysts in alkaline media. Meanwhile, its anodic current remains ≈50% even after a 4 h durability test at 0.53 V versus RHE. As for the C1‐pathway selectivity, in situ infrared adsorption spectral (IRAS) results demonstrate that it could significantly improve the production of CO2. More directly, the apparent faraday efficiency of EOR C1 pathway is estimated to be as high as 20% (at 0.53 V versus RHE). This Rh–Pb catalyst could hold great promise for developing the commercial DEFCs.