Abstract Treatment of divalent (ONNO)V(TMEDA) ( 1 ; ONNO=[2,4‐Me 2 ‐2‐(OH)C 6 H 2 CH 2 ] 2 N(CH 2 ) 2 NMe 2 ) with CO 2 afforded [(ONNO)V] 2 (μ‐OH)(μ‐formate) ( 2 ). Whereas the bridging hydroxo and formate groups both originated from CO 2 , the H atoms present on the two residues were obtained through H‐atom radical abstraction from the solvent. DFT calculations revealed an initially linear CO 2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the so‐formed oxo group and an additional bridging CO 2 residue in promoting radical behavior.