This study was to evaluate the effect of different water amounts and hydrolysis times of silane coupling agent on shear bond strength between lithium disilicate glass ceramic (LDS) and composite resin. Fourteen groups (n=7) of different water amounts (90, 50 and 10%v/v) and hydrolysis times (5, 19, 75 and 300 s) of experimental silane coupling agent that were prepared for silanization, non-silanization and commercial silane coupling agent (CSC) groups. Two-way analysis of variance (ANOVA) revealed no interaction between water amounts and hydrolysis times of ESC on shear bond strength between LDS and composite resin. One-way ANOVA exhibited the highest shear bond strength and the highest mean percentage in mixed failure mode in the 50%v/v group. Molecular analysis of ¹³C and ²⁹Si indicated that nuclear magnetic resonance spectra of M2 and M3 hydrolysis species were found in 50%v/v group. The presenting of M2 and M3 which was predominant factor contributing to the highest shear bond strength.