To avoid the agglomeration of iron NPs and improve the dispersion of Fe SAs, we employed a mixed-ligand strategy to regulate the iron content in PCN-224(ZnxFey) and PCN-222(ZnxFey). Thanks to the sublimation of Zn and the Kirkendall effect, uniform dispersions of Fe SAs with 1.04-1.06 wt% were obtained in the pyrolysis products Zn0.5Fe0.5-N-C-224 and Zn0.5Fe0.5-N-C-222 with excellent CO2 → CO activity, super-stability, and recyclability.