Proton exchange membrane fuel cells (PEMFC) are vulnerable to oxygen starvation when working under variable load. To address these issues, a cascade control strategy of sliding mode control (SMC) and Proportion Integration Differentiation (PID) control is proposed in this study. The goal of the control strategy is to enhance the PEMFC’s net power by adjusting the oxygen excess ratio (OER) to the reference value in the occurrence of a load change. In order to estimate the cathode pressure and reconstruct the OER, an expansion state observer (ESO) is developed. The study found that there is a maximum error of about 2200Pa between the estimated cathode pressure and the actual pressure. Then the tracking of the actual OER to the reference OER is realized by the SMC and PID cascade control. The simulation study, which compared the control performance of several methods—including PID controller, adaptive fuzzy PID controller and the proposed controller, i.e., the SMC and PID cascade controller—was carried out under various load-changing scenarios. The outcomes demonstrate that the proposed SMC and PID cascade controller method really does have a faster response time. The overshoot is reduced by approximately 3.4% compared to PID control and by about 0.09% compared to fuzzy adaptive PID. SMC and PID cascade control reference OER performs more effectively in terms of tracking compared to PID control and adaptive fuzzy PID control.