The application of ultrashort pulse lasers for precision material processing has been an active area of fundamental and applied research due to their unique properties. When an ultrashort laser pulse interacts with a solid target, the electrons are heated to a high temperature by the absorption of laser energy. By the electron-phonon interactions, the hot electrons transfer energy to the lattice. For the femtosecond laser pulse, energy is transferred to the electrons on a time scale much faster than the transfer time of this energy to the lattice of the material and then the time of further propagation of heat along the sample surface. The latter results in a much smaller lateral thermal damage or heataffected zone if compared with longer pulses impact. In this paper we present the results of femtosecond laser annealing of PZT film. Since the laser beam is Gaussian, the temperature at the laser spot varies within the illuminated area, which results in an annealed area much smaller than the beam diameter. In this way a diffraction limit can be overcome, and nanosize perovskite structures can be formed. Several techniques were used to confirm formation of perovskite ferroelectric structure: in-situ during annealing second harmonic generation, confocal and near-field non-linear optical microscopy and piezo-force microscopy. SHG technique of detection the annealing process is based on the changing of symmetry of the film from centrosymmetric (amorphous) to non-centrosymmetric (perovskite). Since the leading electrodipole order SHG is allowed only in non-centrosymmetric media, the SHG intensity behavior during annealing let us detect the transition the PZT film to perovskite phase. Except observing time dependence of SHG intensity during annealing, after annealing we performed so called SHG scanning of the film area including annealed region. The observed SHG peak allowed us not only to confirm formation of perovskite ferroelectric structure, but also to estimate the diameter of the annealed area. Novel nanoscale tools are indeed needed to characterize ferroelectric switching and other electrical properties in the annealed microregions which is very difficult to do by conventional methods as the size of the focused beam is small. Piezo-force microscopy technique allows us to investigate local electromechanical properties of annealed area, including domain switching dynamics.