Direct ethanol fuel cells have garnered considerable attention owing to their minimal pollution, high energy density and diverse fuel sources. However, the slow anodic ethanol oxidation reaction has limited its large-scale application. In this work, the green self-reduction method of Co2(CO)8 as precursor and reducing agent is used to design PdCo bimetallene for ethanol oxidation reaction. The ultra-thin porous nanosheet structure of PdCo bimetallene leads to its abundant defects, facilitating increased active sites and enhanced electrical conductivity. The findings demonstrate substantial enhancements in both the activity and stability of the catalyst. The mass activity of PdCo bimetallene reached 1.58 A mg−1, marking a 2.8-fold increase compared to Pd black. Moreover, the catalyst maintained no less than 98% of the initial current over five consecutive 4000 s chronoamperometric tests, highlighting its remarkable stability. This work provides a green self-reduction synthesis strategy for the preparation of defect-rich bimetallene for ethanol electrocatalytic applications.