In this work, cobaloxime molecules have been synthesized in our group, and new photoinduced hydrogen production systems have been constructed. Based on the new systems for hydrogen production, the mechanism of electron transfer as well as system degradation have been investigated in detail. According to the simulation results in Gaussian 03 software, we implement the ideal catalytic process for hydrogen production induced by cobaloxime. In cobaloxime molecular, Co is indeed the catalytic center, that is to say, it is the change of electrovalence of Co atoms from 3 to 2 and 1, and then from 1 to 3, implies the catalytic process. Through the simulation, we can obtain the middle products in the catalytic process clearly. Moreover, the electron charge of middle products can be analyzed, based on which the catalytic pathway predicted by other experimental results is confirmed. All this provides the theoretical basis for the hydrogen production catalyzed by cobaloxime molecular.