PbTiO3 thin films have been prepared by ultraviolet (UV)-assisted rapid thermal processing (RTP) (photochemical solution deposition) following a sol–gel method. To prepare photo-sensitive sols, two types of photo-initiators compounds, N-methyldiethanolamine and propylenaldehyde, have been incorporated into the system. The effect of the type and amount of photo-initiator on the UV light absorption of the respective precursor solutions was studied. At 400°C, the PbTiO3 perovskite phase was observed by X-ray diffraction in the films. These films show an improved ferroelectric response when they are UV-irradiated during the annealing as compared with those nonirradiated. Moreover, properties are significantly better in PbTiO3 thin films prepared by using N-methyldiethanolamine as a photoinitiator. Thus, films prepared from sols containing N-methyldiethanolamine, UV-irradiated and crystallized by RTP at 400°C, show well-defined ferroelectric hysteresis loops with values of remnant polarization and coercive field of Pr∼11.9 μC/cm2 and Ec∼235 kV/cm, respectively.