Enhancing Hydrogen Embrittlement Resistance of Al–Zn–Mg–Cu Alloys via Si Microalloying and Optimized Heat Treatment

7xxx series aluminum alloys are critical structural materials in aerospace applications, but their susceptibility to hydrogen embrittlement (HE) poses significant challenges to service safety and durability. The effects of Si, Er, and Zr microalloying, combined with optimized heat treatments on the HE resistance of Al–Zn–Mg–Cu alloys, were systematically investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and mechanical testing. Three alloys—1# (AlZnMgCuZr), 2# (AlZnMgCuErZr), and 3# (AlZnMgCuSiErZr)—were subjected to single-stage or two-stage homogenization, followed by solution treatments at 470 °C/2 h and 540 °C/1 h, and peak aging at 125 °C. The hydrogen charging experiment was conducted by first applying a modified acrylic resin coating to protect the gripping sections of the specimen, followed by a tensile test. Results demonstrate that alloy 3# with Si addition exhibited the lowest RAloss, followed by the 2# alloy, which effectively improved the alloys’ hydrogen embrittlement behavior. Compared with the solution in 470 °C/2 h, the 540 °C/1 h solution treatment enabled complete dissolution of Mg2Si phases, promoting homogeneous precipitation and peak hardness comparable to alloy 2#. Two-stage homogenization significantly enhanced the number density and refinement of L12-structured Al3(Er,Zr) nanoprecipitates. Silicon further accelerated the precipitation kinetics, leading to more Al3(Er,Zr) nanoprecipitates, finely dispersed T′/η′ phases, and lath-shaped GPB-II zones. The GPB-II zones effectively trapped hydrogen, thereby improving HE resistance. This work provides a viable strategy for enhancing the reliability of high-strength aluminum alloys in hydrogen-containing environments.