Various alloys demand customized etchants due to their diverse chemical compositions, particularly in the realm of aluminum alloys. Consequently, in this study, a technique is proposed for metallographic visualization of small grain structures within Al–Mg–Zn–(Cu) crossover alloys. In this method, a thermal pretreatment combined with an etching process is relied on. In the study, it is primarily sought to comprehend how grain-boundary precipitation affects etchability, addressing the complexities of characterizing these alloys. The demonstrated approach facilitates the swift assessment of grain sizes <10 μm using light optical microscopy. Exploring the etchability of Al–Mg–Zn–(Cu) crossover alloys across a standard heat-treatment pathway identifies the optimal treatment and suitable etchant for grain visualization. Through process refinement, a reduction in processing time is achieved by employing a single-step preheat treatment lasting 20 min at 180 °C post solution annealing. Transmission electron microscope analysis reveals continuous occupancy of the grain boundary with T-phase as the key factor influencing the alloy's etchability. Grain size assessment involves line intercept counting and equivalent circle diameter measurement for precise characterization.