Polyethylene glycol (PEG) 2000 was used as a templating reagent to synthesize porous TiO₂ thin film by sol–gel process. The nanopores resulting from the presence of growing cracks were ultimately formed on the surface when PEG content was higher than the critical value. Surprisingly, stable pore structure disappeared and surface became fluctuating and dehiscent after PEG amount increased to 0.02 M. Besides, two main hypotheses were proposed in order to explain this superhydrophilic behavior, namely the Wenzel and Cassie wetting impregnating models. Furthermore, the transition between these two wetting regimes was investigated and the criteria for the design and construction of Cassie impregnating wetting surface was also discussed. It was found that Cassie state shifting from Wenzel state could be easily achieved with increasing hole depth on TiO₂ surface. The study of transition between Wenzel and Cassie impregnating wetting regimes on porous films provides valuable wetting mechanism of porosity-driven wettability for the design of superhydrophilic surfaces.