采用循环伏安法和线性扫描法研究了硫酸和甲磺酸介质中Ce3+/Ce4+在Pt旋转圆盘电极（RDE）上的电化学性能，初步探索了Ce3+/Ce4+的络合行为，考察了Ce3+反应的交换电流密度、扩散系数以及反应速率常数，比较了两种酸介质中Ce3+在Pt电极氧化的活化能. 结果表明，硫酸介质中以Ce4+的络合为主，其平衡电位负移；甲磺酸介质中以Ce3+的络合为主，其平衡电位正移. 硫酸介质中Pt电极上Ce3+更容易氧化为Ce4+, 硫酸铈(III)的电氧化对温度更为敏感. ; The electrochemical oxidations of Ce3+ to Ce4+ on Pt rotating disk electrode (RDE) in both sulfuric acid and methanesulfonic acid (MSA) solutions were studied by using cyclic voltammetry and linear sweep voltammetry. The complexing behaviors of Ce3+/Ce4+ were preliminarily probed and the exchange current density, diffusion coefficient, as well as reaction rate constant were obtained from Butler-Volmer equation. The activation energies of Ce3+ oxidation on Pt electrode in two types of acidic media, obtained from Arrhenius equation, were also compared. The results indicate that Ce3+ can be oxidized to Ce4+ much easier in sulfuric acid than in MSA solutions. The equilibrium potential in sulfuric acid solutions moves negatively due to the predominant complexation of Ce4+, while that in MSA solutions positively because of the predominant complexation of Ce3+, The larger values of activation energy for the oxidation of Ce3+ to Ce4+ on Pt electrode in sulfuric acid solutions suggest that the oxidation of Ce3+ occurs more readily and the electro-oxidation of cerous sulfate is more susceptible to temperature. ; 浙江省研究生教育创新基地基金项目（No. 1001）资助 ; 作者联系地址：浙江工业大学 绿色化学合成技术国家重点实验室培育基地，浙江 杭州 310014 ; Author's Address: State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China ; 通讯作者E-mail：science@zjut.edu.cn