Using dc on-axis magnetron sputtering and pulsed laser deposition, we have grown thin films of La0.67Sr0.33MnO3 (LSMO) on (001) MgO substrates exhibiting a sizeable increase of the metal–insulator transition temperature. In spite of large lattice misfit (8%) between the LSMO film and the substrate structural analyses reveal an epitaxial growth of the films with different crystal structures depending on the used deposition techniques. This work provides structural and electrical characterizations of the LSMO films suitable for further practical applications operating at room temperature.