All-ceramic restorations are the foundation of modern esthetic dentistry. Clinical approaches for preparation, durability, aesthetics, and repair have been reformed by the idea of adhesive dentistry. The aim of the study and the objective question was to evaluate the impact of heated hydrofluoric acid pretreatment and the application technique’s influence on the surface morphology and roughness of leucite-reinforced glass–ceramic materials (IPS Empress CAD, Ivoclar Vivadent), which is fundamental for understanding the adhesive cementation process. Scanning electron microscopy was used to observe the effectiveness of the two HF (Yellow Porcelain Etch, Cerkamed) application techniques and the HF’s temperature impact on the surface topography of the ceramic. Based on surface conditioning methods, the adhesive cement (Panavia V5, Kuraray Noritake Dental Inc., Tokyo, Japan) was applied to the conditioned ceramic samples and light-cured. Shear bond strength values were correlated with the micro-retentive surface texture of the ceramic. With universal testing equipment at a 0.5 mm/min crosshead speed, SBS values between the resin cement and the ceramic material were assessed until failure. Analyzing the fractured surfaces of the specimens by digital microscopy, the failure modes were divided into three categories: adhesive, cohesive, and mixed failure. Analysis of variance (ANOVA) was used to statistically analyze the collected data. The results show that alternative treatment methods affected the material’s surface characteristics and have an influence on the shear bond strength.