Ionic liquids based on 1-butyl-3-methylimidazolium hexafluoro-phosphate (ILs [Bmim][PF6]) has been employed to wet the mesoporous and dense titanium dioxide (TiO2) films. It has been found from atomic force microscopy (AFM) analysis that ILs [Bmim][PF6] can form a wetting phase on mesoporous TiO2 films, but nonwetting and sphere shaped droplets on dense films. AFM topography, phase images, and adhesion measurements suggest a remarkable dependence of wetting ILs [Bmim][PF6] films on the TiO2 porous geometry. On mesoporous TiO2 films, the adhesive force of ILs [Bmim][PF6] reaches at 40 nN, but only 4 nN on dense TiO2 films. The weak interacting ILs [Bmim][PF6] on dense TiO2 films forms rounded liquid spheres (contact angle as 40°), which helps to reduce friction locally but not on the whole surface. The stronger adhesive force on mesoporous TiO2 films makes ILs [Bmim][PF6] adhere to the surface tightly (contact angle as 5°), and this feature remains after five months. The stable spreading ILs [Bmim][PF6] films provide low friction coefficient (0.0025), large wetting areas, and short CO2 diffusion distance on the whole mesoporous TiO2 surface, avoiding the significant decelerating effect through equilibrium limitations to enable CO2 capture rate up to 1.6 and 10 times faster than that on dense TiO2 and pure ILs, respectively. And importantly, ILs wetted on mesoporous TiO2 shorten the time reaching to the maximum adsorption rate (2.8 min), faster than that on mesoporous TiO2 (6.1 min), and dense TiO2 (11.2 min). This work provides an important guidance for the improvement of the efficiency of CO2 capture, gas separation, and the lubrication of micro/nanoelectromechanical systems (M/NEMs).