Abstract: The electrochemical behavior of Ce（Ⅲ） on the both liquid Ga pool and film Ga electrode is investigated by the various transient methods including of cyclic voltammetry(CV), square wave voltammetry(SWV), and chronopotentiometry(CP). The results show that Ce（Ⅲ） is reduced into αGa₆Ce by one step process on liquid Ga pool cathode: Ce（Ⅲ）+3e+6Ga=αGa6Ce, and the reaction is irreversible and diffusion-controlled. The relationship between the diffusion coefficient of Ce（Ⅲ） and the temperature can be calculated as: ln D=2.88-10 118.4/T. The temperature dependence of the half-wave potential for Ce（Ⅲ）/αGa₆Ce is determined to be: E=-1.701+5.472×10^-4T. On the film Ga electrode, at least three kinds of intermetallic compounds are observed.