Rhodium-catalyzed acrylate synthesis from CO 2 and ethylene was accomplished by using a guanidine-based NCN pincer ligand. The repulsion between pπ-electron of guanidine sidearms and occupied dπ orbital of rhodium center raised the level of d-electrons close to those of formerly known d 8 -ruthenium catalyst, thereby promoting the metal-lalactone formation from carbon dioxide and ethylene. This work fills the absence of group-9 metal based catalyst for the acrylate synthesis and provides a designing approach for pincer-ligated d 8 -metal catalysts to utilize pπ-dπ interaction for promoting desirable redox processes.