Mass spectrometric analysis of the anionic products of interaction between bimetallic palladium-copper tetrahydride anions, PdCuH₄^-, and carbon dioxide, CO₂, in a reaction cell shows an efficient generation of the PdCuCO₂H₄^- intermediate and formate/formic acid complexes. Multiple structures of PdCuH₄^- and PdCuCO₂H₄^- are identified by a synergy between anion photoelectron spectroscopy and quantum chemical calculations. The higher energy PdCuH₄^- isomer is shown to drive the catalytic hydrogenation of CO₂, emphasizing the importance of accounting for higher energy isomers for cluster catalytic activity. This study represents the first example of CO₂ hydrogenation by bimetallic hydride clusters.