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A novel method was developed to produce a TiO₂ film with circular pores on its surface. The pores aroused from the precursor solution using both acetylacetone (AcAc) and diethanolamine (DEA) as stabilizers. The appearance of interconnected or isolated pores for the films was discussed in relation to the phase separation in the sol–gel process with the presence of Acac and DEA. Macropore size, together with connectivity of pores and gel skeleton, can be controlled by selecting an appropriate composition for preparation at DEA amount or regulating a time scale of the sol–gel transition. Finally, wetting behavior of the resulting films was characterized by using contact angle measurements. The TiO₂ films with interconnected or relatively isolated pores exhibit superhydrophilic characteristic, although it is not exposed to ultraviolet irradiation. Deducing from the Wenzel–Cassie regimes’ transition criterion, the existence of Cassie impregnating wetting regime rather than Wenzel one upon these porosity-driven superhydrophilic surfaces can be obtained.