Thin films of LaFeO3 for photocatalytic applications were grown by Pulsed Laser Deposition on a flexible polycrystalline Tetragonal Yttria Stabilized Zirconia substrate (T-YSZ). Their structure and morphology were investigated using scanning electron microscopy, transmission electron microscopy, high-angle annular darkfield scanning transmission electron microscopy (STEM), energy dispersive spectroscopy available in the STEM system, X-ray diffraction, and Raman spectroscopy techniques. The band gap energies and the life time of the charge carrier were deduced from UV-Vis and time resolved fluorescence spectroscopies. The polycrystalline substrate T-YSZ was homogeneously covered by the LaFeO3 films, even at the substrate grain boundaries. The surface of the films presents a nanostructuration with flat ended and tip ended grains. The exposed facets are mainly {100}C. Atomic–scale microstructure investigations revealed twins in LaFeO3 grains, as consequence of the curvature of the T-YSZ substrate. Chemical analyses showed iron and oxygen deficiency in the LaFeO3 layers. Two optical transitions with energies of 1.9 eV and 2.5 eV corresponding to visible light absorption were evidenced, and the average life time of charges carriers was found to be 5 ns.