The hydrosilylation of CO2 with different silanes such as HSiEt3, HSiMe2Ph, HSiMePh2, HSiMe(OSiMe3)2, and HSi(OSiMe3)3 in the presence of catalytic ammounts of the iridium(III) complex Ir(H)(CF3CO2)(NSiN*)(coe) (1; NSiN*=fac‐bis‐(4‐methylpyridine‐2‐yloxy); coe=cis‐cyclooctene) has been comparatively studied. The activity of the hydrosilylation catalytic system based on 1 depends on the nature of the reducing agent, where HSiMe(OSiMe3)2 has proven to be the most active. The aforementioned reactions were found to be highly selective toward the formation of the corresponding silylformate. It has been found that using 1 as catalyst precursor above 328 K decreases the activity through a thermally competitive mechanistic pathway. Indeed, the reduction of the ancillary trifluoroacetate ligand to give the corresponding silylether CF3CH2OSiR3 has been observed. Moreover, mechanistic studies for the 1‐catalyzed CO2‐hydrosilylation reaction based on experimental and theoretical studies suggest that 1 prefers an inner‐sphere mechanism for the CO2 reduction, whereas the closely related Ir(H)(CF3SO3)(NSiN)(coe) catalyst, bearing a triflate instead of trifluoroacetate ligand, follows an outer‐sphere mechanism. Too hot to go outside: A mechanism explaining the iridium‐catalyzed hydrosilylation of CO2 is proposed. It was found that the 1‐catalyzed CO2‐hydrosilylation depends on the nature of the silane. Moreover, the phenomenon of decreasing activity and selectivity of the catalytic system with increasing reaction temperature has been clarified using computational methods.