Hydrofluoric acid (HF) is commonly used as an etchant for the pretreatment of dental computer-aided design/computer-aided manufacturing (CAD-CAM) materials, such as glass-ceramics and resin composites. Despite its effectiveness, the harmful and hazardous nature of HF has raised significant safety concerns. In contrast, ammonium fluoride (AF) is known for its relatively low toxicity but has limited etching capability. This study explored the potential of ammonium hydrogen sulfate (AHS), a low-toxicity and weak acid, to enhance the etching ability of aqueous AF solutions for the bonding pretreatment of CAD-CAM materials. This study investigated five types of aesthetic CAD-CAM materials: lithium disilicate glass, feldspathic porcelain, polymer-infiltrated ceramic networks, resin composites, and zirconia. Seven experimental etchants were prepared by varying the amount of AHS added to aqueous AF solutions, with each etchant used to etch the surfaces of the respective CAD-CAM materials. The treated surfaces were analyzed using scanning electron microscopy and confocal laser scanning microscopy. Additionally, the shear bond strength (SBS) of the CAD-CAM materials treated with a luting agent (resin cement) was evaluated. The results indicated that the AF1/AHS3 (weight ratio AF:AHS = 1:3) etchant had the most substantial etching effect on the surfaces of silica-containing materials (lithium disilicate glass, feldspathic porcelain, polymer-infiltrated ceramic networks, and resin composites) but not on zirconia. The SBS of the materials treated with the AF1/AHS3 etchant was comparable to that of the commercial HF etchant. Hence, an AF/AHS mixed solution could effectively etch silica-containing CAD-CAM materials, thereby enhancing their bonding capabilities.