A series of (benzoimidazol-2-ylmethyl)amine palladium(II) complexes have been employed as catalysts in the homogeneous hydrogenation of alkenes and alkynes under mild conditions. A correlation between the catalytic activity and the nature of the ligand was established. Kinetic studies of the hydrogenation reactions of styrene established pseudo-first-order dependence on styrene substrate. On the other hand, partial orders with respect to H2 and catalyst concentrations were obtained. The nature of the solvent used influenced the hydrogenation reactions, where coordinating solvents resulted in lower catalytic activities. Kinetics and mechanistic studies performed were consistent with the formation of palladium monohydride intermediates as the active species.