Dynamic behavior of semibatch processes were numerically investigated for catalytic hydrogenation of diene polymers/copolymers, including 1,4-polybutadiene (PB), diblock (SB) and triblock (SBS) copolymers of styrene and butadiene, and nitrile-butadiene rubber (NBR). Generalized models of the kinetic mechanism for;homogeneous catalytic hydrogenation and of coupling behaviors between kinetics and mass transfer were developed for semibatch processes. The sensitivity of various kinetic parameters and the effects of operation conditions on the hydrogenation processes were analyzed, and the evolution of reaction trajectories in the semibatch hydrogenation processes was studied. It is proposed that the coupling behavior between the catalytic hydrogenation and mass transfer was completely determined by the ability of the catalyst in activating hydrogen, carbon-carbon double bond loading level, and the relative capacity of reaction to mass transfer. Three dimensionless parameters were derived to characterize these aspects. An optimal operation surface composed of the proposed three dimensionless parameters was constructed. Further research directions are suggested.