The fastening bolt is one of the important parts of the stacked structure proton exchange membrane electrolyzer (PEMEC), and the bolt tightening behavior has a significant impact on the electrochemical performance of the PEMEC. In this paper, we use a transparent visualization system to explore the effect of tightening bolt behavior on the performance of PEMEC. Pressure sensitive paper was used to record the contact pressure distribution map of PEMEC under different bolt tightening methods, and a high-speed camera was used to record the state of gas-liquid two-phase flow inside PEMEC under different bolt tightening methods. Both of them are used to verify the effect of bolt tightening behavior on the performance of PEMEC. The experimental results show that the contact pressure of PEMEC increases with the increase of bolt torque, and the electrochemical performance first increases and then decreases with the increase of bolt torque. The optimum bolt torque is 3.5 N m for a square PEMEC with an end plate size of 100 mm × 100 mm and a membrane size of 50 mm × 50 mm × 0.17 mm. The PEMEC performance increases with the increase of bolt tightening steps, and the optimal tightening step for the system is three steps. In addition, symmetrical tightening of bolts is beneficial for improving electrochemical performance, and there is an optimal tightening sequence in the system. This paper illustrates the relationship between tightened bolts and PEMEC electrochemical performance, showing the relationship between bolt tightening and the gas-liquid two-phase flow state inside PEMEC. The research results can provide a reference for optimizing the assembly and installation process of PEMEC.