Protonolysis of ZnH2n with the conjugated Brønsted acid of the bidentate diamine TMEDA (N,N,N′,N′‐tetramethylethane‐1,2‐diamine) and TEEDA (N,N,N′,N′‐tetraethylethane‐1,2‐diamine) gave the zinc hydride cation (L2)ZnH+, isolable either as the mononuclear THF adduct (L2)ZnH(thf)+BArF4− (L2=TMEDA; BArF4−=B(3,5‐(CF3)2‐C6H3)4−) or as the dimer {(L2)Zn)}2(μ‐H)22+BArF4−2 (L2=TEEDA). In contrast to ZnH2n, the cationic zinc hydrides are thermally stable and soluble in THF. (L2)ZnH+ was also shown to form di‐ and trinuclear adducts of the elusive neutral (L2)ZnH2. All hydride‐containing cations readily inserted CO2 to give the corresponding formate complexes. (TMEDA)ZnH+BArF4− catalyzed the hydrosilylation of CO2 with tertiary hydrosilanes to give stepwise formoxy silane, methyl formate, and methoxy silane. The unexpected formation of methyl formate was shown to result from the zinc‐catalyzed transesterification of methoxy silane with formoxy silane, which was eventually converted into methoxy silane as well. Insoluble, thermally unstable zinc dihydride ZnH2n can be converted into robust zinc hydride cations (L2)ZnH+ which catalyze the homogeneous hydrosilylation of CO2 to give methoxy silane. Ligand L2 can be as simple as chelating TMEDA.