Density functional theory calculations have been performed to investigate the molecular mechanism of the hydrogenation reactions of 1,1-diphenylethylene and myrcene catalyzed by the actual calcium hydride catalyst, CaH(dipp-nacnac)(thf) (dipp-nacnac = CH{(CMe)(2,6-iPr(2)-C6H3N)}(2)). The hydrogenation reactions of these two alkenes proceed via a similar pathway, which includes three steps. First, the hydride migrates from the calcium center to one olefinic carbon in the substrate. Then, the hydride transfer product can easily transform into a key ion-pair intermediate. This intermediate provides an intramolecular frustrated Lewis pair, in which the calcium center acts as a Lewis acid, and one olefinic carbon acts as a Lewis base. Next, the H H bond is heterolytically cleaved by this Lewis pair through a concerted Lewis acid Lewis base mechanism, producing the hydrogenation product regenerating the catalyst. For these two reactions, the rate-limiting step is the hydride transfer step, with free barriers of 29.2 kcal for both substrates. In addition, our calculations indicate that the hydrogenation reaction of 1,1-diphenylethylene catalyzed by the analogous strontium hydride complex may readily occur, but the similar hydrogenation reaction is less likely to take place under similar conditions as adopted by the hydride catalyst. The results can give satisfactory descriptions of experimental facts observed for these two reactions. The hydrogenation mechanism proposed here is different from that of the late transition alkene hydrogenation or the organolanthanide-catalyzed alkene hydrogenation.