Highly crystalline epitaxial Ba0.8Sr0.2TiO3 (BST) thin-films are grown on (001)-oriented LaNiO3-buffered LaAlO3 substrates by pulsed laser irradiation of solution derived barium-zirconium-titanium precursor layers using a UV Nd:YAG laser source at atmospheric conditions. Thestructural analyses of the obtained films, studied by X-ray diffractometry and transmission electron microscopy, demonstrate that laser processing allows the growth of tens of nm-thick BST epitaxialfilms with crystalline structure similar to that of films obtained through conventional thermal annealing methods. However, the fast pulsed nature of the laser employed leads tocrystallization kinetic evolution orders of magnitude faster than in thermal treatments. The combination of specific photothermal and photochemical mechanisms is the main responsible for the ultrafast epitaxial laser-induced crystallization. Piezoresponse microscopy measurements demonstrate equivalent ferroelectric behavior in laser and thermally annealedfilms, being the piezoelectric constant ∼25 pm V−1.