Reaction of dibenzyl calcium complex Ca(Me4TACD)(CH2Ph)2, containing the neutral NNNN‐type macrocyclic ligand Me4TACD (Me4TACD=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane), with triphenylsilane gave the cationic dinuclear calcium hydride Ca2H2(Me4TACD)2(PhCHSiPh3)2 which was characterized by NMR spectroscopy and single‐crystal X‐ray diffraction. The cation can be regarded as the ligand‐stabilized dimeric form of hypothetical CaH+. Hydrogenolysis of benzyl calcium cation Ca(Me4TACD)(CH2Ph)(thf)+ gave dicationic calcium hydrides Ca2H2(Me4TACD)2BAr42 (Ar=C6H4‐4‐tBu; C6H3‐3,5‐Me2) containing weakly coordinating anions. In THF, they catalyzed the isotope exchange of H2 and D2 to give HD and the hydrogenation of unactivated 1‐alkenes. The solution is calcium hydride: The cationic dinuclear calcium hydride Ca2H2(Me4TACD)22+ was characterized by NMR spectroscopy and single‐crystal X‐ray diffraction. The complex catalyzes the HD exchange between H2 and D2 as well as the hydrogenation of unactivated 1‐alkenes.