In the present study, the adhesive properties and initial deposition processes of electrolessdeposited Cu films to glass substrates in detail. The adhesive strengths of Cu thin films which were electrolessdeposited on the glass substrates were evaluated by adhesive tape test, while their surface structures were analyzed by using TEM. We used two-step catalyzation (sensitization-activation) method for pretreatment of electrolessdeposition onto glass substrates. The catalyst distribution can be made to vary. The adhesive strength of Cu films tends to increase with decreasing SnCl2 concentration in sentitizer and increased with increasing surface roughness of glass substrates. In order to specify the exfoliation site, the quantitative analysis of Sn and Pd on the exfoliated film and the substrate was investigated by XPS. XPS analysis showed that Sn and Pd existed on the exfoliated films and only Sn existed on the substrates. The results indicated that the exfoliation of all the films electrolessdeposited on glass substrates occurred in the interface between the Sn adsorbates and the Pd adsorbates. The drying pretreatment after activation improved adhesive strength.