The effects of variable outer temperatures on the Pressure Swing Adsorption (PSA) performance was investigated for hydrogen separation from multicomponent mixtures. Linear driving force (LDF) model was used to describe mass transfer between two phases. Coupled Langmuir isotherm was used for each component as a nonlinear adsorption isotherm. In order to consider the influence of temperature, energy balance was set up along with mass balance equation. The results indicated the importance of outer temperature in this process. According to variable outer temperature, bed temperature and concentration of hydrogen were changed and finally separation performance on purity and recovery was influenced.