The dual-active hybrid full-bridge (H-FDAB) DC–DC converter has great potential in medium-voltage high-power photovoltaic power station applications by introducing a three-level bridge arm to increase the output voltage range. However, its mathematical model and optimum modulation schemes have not been fully explored. Under the traditional PI control, the H-FDAB DC–DC converter will produce significant reflux power, which will lead to a decrease in converter efficiency and output voltage fluctuation. On this basis, this paper proposes a reflux power optimization strategy for an H-FDAB DC-DC converter based on active disturbance rejection control (ADRC). Firstly, the structure and power characteristics of the H-FDAB DC–DC converter are analyzed, and the relationship among the reflux power, the transmission power, and the phase shift angle is derived. Secondly, to reduce the complexity of the control calculation, upon the foundation of dual phase-shifting modulation, the Karush–Kuhn–Tucker (KKT) condition is used to solve for the phase shift angle that corresponds to the minimum reflux power. Simultaneously, we develop an ADRC loop utilizing an extended state observer (ESO) for the real-time estimation of system states. We also consider the sudden changes in input voltage, load switching, and transmission power fluctuations caused by reflux power optimization strategies as system disturbances and compensate for them accordingly. Finally, the experiments conclusively validate the designed control strategy’s correctness and feasibility.