The epitaxial growth of Ce0.9Zr0.1O2–y (CZO) thin-films on yttria-stabilized zirconia (YSZ) (001) single crystal and YSZ (001)/stainless steel (YSZ/SS) technological substrates is investigated by pulsed laser irradiation of solution-derived cerium–zirconium precursor layers using a UV Nd:YAG laser source at atmospheric conditions. The influence of laser processing parameters on the morphological and structural properties of the obtained films is studied by atomic force and transmission electron microscopies, as well as X-ray diffractometry. The analyses performed demonstrate that laser treatments enable the epitaxial growth of tens of nanometers thick CZO films with a crystallization kinetic process several orders of magnitude faster than that of conventional thermal annealing. Fully epitaxial films are attained using stainless steel (SS) flexible tapes as a substrate. Even though photochemical mechanisms are not fully discarded, it is concluded that photothermal processes are the main contribution responsible for the fast epitaxial crystallization.