Understanding the tensile strength and failure mechanism of rock–cement interfacial transition zone (ITZ) is of vital significance to the sealing integrity of cement sheath under downhole condition. Taking advantage of multiple techniques, i.e., digital image correlation (DIC), nano-indentation, XRD-Rietveld analysis, 29Si MAS solid NMR, and SEM-EDX, this study is devoted to investigating the impacts of curing temperature, rock type, and the addition of nano-silica (NS), on the tensile strength and failure mechanism of rock–cement sample. The experimental results show that both the curing temperature and the addition of NS leads to the formation of more C-S-H, which densifies the ITZ microstructure and responsible for high tensile strength of rock–cement samples; the tensile strengths of shale-cement samples are consistently higher than those of sandstone-cement sample; the crack velocities for rock–cement samples under three-point bending tests are approximately 1 mm/s, the crack velocities for rock–cement samples are slowed down when the NS is incorporated in cement paste, but they are independent on the rock type and curing temperature.