In the present paper a detailed investigation of a well known photoreaction, i.e. phenol photodegradation in the presence of TiO2, has been carried out. The Fourier transform infrared (FT-IR) technique has been used to characterize the catalyst surface and to follow the photoprocess by "in situ" measurements in a gas-solid regime, simulating the aqueous liquid-solid regime in which this photodegradation reaction has been usually carried out. The influence on the photoprocess of the surface hydroxylation of the catalyst has been investigated and the presence of some reaction intermediates has been revealed by FT-IR. The experimental results have demonstrated that the chosen gas-solid system in the presence of water vapour is an acceptable simulation of the aqueous liquid-solid regime.