The aim of this study is to visualize and characterize by ultra-high-speed imaging (UHSI) the failure phenomena at the resin–ceramic bonding interface of lithium disilicate (LiSi2) samples bonded with gold-standard protocol (Monobond Plus [MB]) and the nontoxic one (Monobond Etch & Prime [MEP]) subjected to mechanical loading. Unprecedented frame rate, image resolution, and recording time were reached by using the most advanced UHSI camera. The finite element analysis (FEA) of the proposed mechanical test confirmed that the specific design of our samples enables a combined shear and compression stress state, prone to test the bonding interface while being close to physiological stresses. Ten LiSi2 samples were pretreated by gold standard (MB, n = 5) and self-etching primer (MEP, n = 5). Axial compression loading gradually increased until catastrophic failure was performed. As shown by the FEA, the angle between the bonding interface and load direction leads to shear–compression stresses at the resin–ceramic bonding interface. Failure was recorded by UHSI at 300,000 fps. All recorded images were analyzed to segregate events and isolate the origin of fracture. For the first time, thanks to the image recording setup, it was observed that debonding is the first event before breakage, highlighting that sample fracture occurs by interfacial rupture followed by slippage and cohesive failure of materials. Failure mode could be described as mixed. MEP and MB showed similar results and behavior.