Crystalline TiO₂ films were prepared on unheated glass substrates by radio frequency (RF) reactive magnetron sputtering at normal angle of incidence (a = 0°) and at glancing angle (a = 87°). The effect of the glancing angle on the structure, microstructure, and wetting properties of the films was investigated. The inclination of the substrate led to phase transformation of the deposited films from rutile to either rutile/anatase or anatase, depending on the working pressure. Extreme shadowing at 87° results in a remarkable increase of the films’ porosity and surface roughness. The mechanism of the glancing-angle-induced crystalline phase formation is thoroughly discussed based on the thermodynamic, kinetic, and geometrical aspects of the nucleation and is related with the microstructural changes. Both crystalline phase and microstructure significantly affect the wetting properties of the TiO₂ films. Glancing-angle-deposited anatase TiO₂ exhibits a high degree of porosity and roughness, a high rate of UV-induced wettability conversion, and a long-term highly hydrophilic nature in dark. Therefore, anatase TiO₂ is potentially a good candidate for applications as dye-sensitized solar cells (DSSC)/perovskite solar cells, microfluidic devices, and self-cleaning surfaces prepared on thermosensitive substrates.