Photoresponsive titania surfaces are of great interest due to their unique wettability change upon ultraviolet light illumination. However, their applications are often limited either by the inability to respond to visible light or the need for special treatment to recover the original wettability. Sensitizing TiO₂ surfaces with visible light-absorbing materials has been utilized in photovoltaic applications. Here we demonstrate that a dye-sensitized TiO₂ surface can selectively change the wettability towards contacting liquids upon visible light illumination due to a photo-induced voltage across the liquid and the underlying surface. The photo-induced wettability change of our surfaces enables external manipulation of liquid droplet motion upon illumination. We show demulsification of surfactant-stabilized brine-in-oil emulsions via coalescence of brine droplets on our dye-sensitized TiO₂ surface upon visible light illumination. We anticipate that our surfaces will have a wide range of applications including microfluidic devices with customizable wettability, solar-driven oil–water clean-up and demulsification technologies.