The aim of this study was to analyze the effect of interfacial covalent bonds on the adhesive behavior of an elastomer, a crosslinked polydimethylsiloxane, and a glass substrate. These covalent bonds were created by applying to both materials an appropriate surface treatment by means of plasma polymerization. Adhesion measurements were carried out by analyzing the contact area between a rubber hemisphere and a flat rigid glass plate. The contact was forced under a given compressive loading for different times tc, then the load was removed and the fracture propagation at the interface was recorded as a function of relaxation time tr. Finally, adhesion energies were also determined by means of a probe test using a tensile testing machine.