The　electroreduction　reaction　of　CO2　(ECO2RR)　requires　high-performance　catalysts　to　convert　CO2　into　useful　chemicals.　Transition　metal-based　atomically　dispersed　catalysts　are　promising　for　the　high　selectivity　and　activity　in　ECO2RR.　This　work　presents　a　series　of　atomically　dispersed　Co,　Fe　bimetallic　catalysts　by　carbonizing　the　Fe-introduced　Co-zeolitic-imidazolate-framework　(C–Fe–Co–ZIF)　for　the　syngas　generation　from　ECO2RR.　The　synergistic　effect　of　the　bimetallic　catalyst　promotes　CO　production.　Compared　to　the　pure　C–Co–ZIF,　C–Fe–Co–ZIF　facilitates　CO　production　with　a　CO　Faradaic　efficiency　(FE)　boost　of　10%,　with　optimal　FECO　of　51.9%,　FEH2　of　42.4%　at　−　0.55 V,　and　CO　current　density　of　8.0 mA cm−2　at　−　0.7 V　versus　reversible　hydrogen　electrode　(RHE).　The　H2/CO　ratio　is　tunable　from　0.8　to　4.2　in　a　wide　potential　window　of　−　0.35　to　−　0.8 V　versus　RHE.　The　total　FECO+H2　maintains　as　high　as　93%　over　10 h.　The　proper　adding　amount　of　Fe　could　increase　the　number　of　active　sites　and　create　mild　distortions　for　the　nanoscopic　environments　of　Co　and　Fe,　which　is　essential　for　the　enhancement　of　the　CO　production　in　ECO2RR.　The　positive　impacts　of　Cu–Co　and　Ni–Co　bimetallic　catalysts　demonstrate　the　versatility　and　potential　application　of　the　bimetallic　strategy　for　ECO2RR.[Figure　not　available:　see　fulltext.].　©　2021,　The　Author(s).