Nanoarchitecture of layer-by-layer (LbL) films is a convenient and simple way to control the photoelectrochemical properties of the semiconductor films. Hereby, we used the combination of polystyrenesulfonate (PSS) and polyethyleneimine (PEI) deposited on the TiO2 film for controlling the photochemical response of the hybrid system. Photogenerated protons on the TiO2 surface are responsible for the acidity change near the irradiated surface. We investigated that the photogenerated protons being absorbed by PEI spatially separated from the TiO2surface with the nanoscale-thick PSS layer (with thickness ca. 5 nm) lead to the sufficient decrease in photoactivity of the hybrid system TiO2/PSS/PEI ca. 4 times in comparison with pristine TiO2. PEI nanolayer being deposited directly on the TiO2 surface can decrease the photoactivity of the system ca. 2–2.5 times.