Aiming at the large time delay characteristics of excimer laser temperature control system, the model identification of excimer laser temperature control system is carried out using MATLAB, and a new Smith-PID prediction compound controller is designed. On this basis, two kinds of controllers are simulated and experimented respectively. Results show that compared with the conventional PID controllers, the overshoot of Smith-PID prediction compound controller is reduced by 41% and the adjustment time is reduced by 51%. The designed controller has the advantages of strong robustness, small overshoot and short adjusting time, which can provide a favorable temperature control environment for the operation of excimer lasers.