In this study, a process for wet metallization on glass substrate involving adhesive electroless plating (ELP) is developed by integrating two material innovations. The first involves functionalizing a polymer-capped Pd nanocluster with amino silane compound to strengthen the adhesion between the ELP metal film and substrate. The second involves an additional nanoscaled TiO2 layer serving as the adhesion promoting layer (APL) coated on glass before metallization. After investigation with various tools, ELP metal film was observed to penetrate the mesoporous structure of TiO2 APL, reinforcing the adhesion of metallized film on glass through the mechanical anchoring effect. The formation of an interlayer between TiO2 APL and glass is not observed. A T-peel strength of 325 N m−1 is achieved. According to fracture analysis, the metal film/TiO2/glass structure breaks inside TiO2 APL, not TiO2 APL/glass, suggesting that further engineering developments are required to improve TiO2 APL coating.