Adhesion and mechanical reliability of silicon/epoxy/polyimide interfaces are critical issues for flexible electronics. Bonds between these interfaces are mainly hydrogen bonds, so their adhesion is weaker than cohesive fracture toughness and vulnerable to moisture. In order to enhance adhesion and suppress moisture-assisted debonding, UV/Ozone treatment and innovative sol-gel derived hybrid layers were applied to silicon/epoxy/polyimide interfaces. The fracture energy and subcritical crack growth rate were measured by using a double cantilever beam (DCB) fracture mechanics test. Results showed that UV/Ozone treatment increased the adhesion, but was not effective for improving reliability against humidity. However, by applying sol-gel derived hybrid layers, adhesion increase as well as suppresion of moisture-assisted cracking were achieved.