ABSTRACT Ionic liquids (ILs) are known to promote the catalytic hydrogenation of CO 2 to formic acid, in particular by shifting the reaction equilibrium through formic acid stabilization. While a broad range of ILs‐formic acid interactions has been described, proposed, and discussed in pure IL systems, the molecular basis for such stabilizing effects is not yet fully understood. Fundamental insights are desired for practically relevant solid catalysts such as those made from supported ionic liqu