Controllable wettability is important for a wide range of applications, including intelligent switching, self-cleaning and oil/water separation. In this work, rapid switching and extreme wettability changes upon ultraviolet (UV) illumination were investigated. TiO2 nanoparticles were modified in solutions of trimethoxy(alkyl)silane, and the suspensions were sprayed on glass substrates. For such samples, the water contact angle (WCA) was shown to transition from a superhydrophobic (WCA ≈ 165°) to a superhydrophilic (WCA ≈ 0°) state within 10 min upon UV illumination and subsequent recovery to superhydrophobicity occurred after heat treatment. It was found that the changes in the trimethoxy(alkyl)silane upon UV illumination can explain the rapid decrease of the WCA from more than 165° to almost 0°. To further investigate the wettability transition, trimethoxy(alkyl)silane and Al2O3 nanoparticles (which are not photocatalytic) were mixed and spray-coated onto the glass substrates as the control samples. Then the unrecoverable change of trimethoxy(alkyl)silane under UV illumination can be confirmed. It was found that the presence of trimethoxy(alkyl)silane in the TiO2–trimethoxy(alkyl)silane coating served to speed up the super-wettability transition time from superhydrophobicity to superhydrophilicity, but also limited the number of wettability recycle times. With this understanding, the effect of the trimethoxy(alkyl)silane concentration on the number of recycle cycles was investigated.