Manganese-catalyzed hydrogenation reactions have attracted broad interest since the first report in 2016. Among the reported catalytic systems, Mn catalysts supported by tridentate PNP- and NNP-pincer ligands have most commonly been used. For example, a number of PNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, aldimines, ketones, nitriles, and esters. Furthermore, various NNP-Mn pincer catalysts have been shown to be active in the hydrogenation of less-reactive substrates such as amides, carbonates, carbamates, and urea derivations. These observations indicated that Mn catalysts supported by NNP-pincer ligands exhibit higher reactivity in hydrogenation reactions than their PNP counterparts. Such a ligand effect in Mn-catalyzed hydrogenation reactions has yet to be confirmed. Herein, we investigated the origin and applicability of this ligand effect. A combination of experimental and theoretical investigations showed that NNP-pincer ligands on the Mn complexes were more electron-rich and less sterically hindered than their PNP counterparts, leading to higher reactivity in a series of Mn-catalyzed hydrogenation reactions. Inspired by the ligand effect on Mn-catalyzed hydrogenations, we developed the first Mn-catalyzed hydrogenation of N-heterocycles. Specifically, NNP-Mn pincer catalysts hydrogenated a series of N-heterocycles (32 examples) with up to 99% yields, and the corresponding PNP-Mn pincer catalysts afforded low reactivity under the same conditions. This verified that such a ligand effect is generally applicable in hydrogenation reactions of both carbonyl and noncarbonyl substrates based on Mn catalysis.