This paper proposes a new process of co-production of MTBE and TBA.The PRO/Ⅱchemical process simulation software is used to carry out steady-state simulation and analysis on this process.The feed temperature and the operating pressure are simulated and optimized through calculating the parameters such as the feed position,the reflux ratio and the theoretical plate number.The results show that the combined production process is reasonable and reliable,and has big practical value with excellent product quality,stable process operations,good economic benefit and nice social benefit.