La2WO6 (LWO) thin films with the a high-temperature orthorhombic polymorph have been grown on (001)-LaAlO3 (LAO) substrates by pulsed laser deposition. The X-ray diffraction study evidences that the films are (001)-oriented. This matching appears to be in good agreement with the compatibility between the alpha-LWO bulk/LAO substrate crystal lattices. Pole figure measurements lead to the following crystallographic relationships between the film and substrate: [100](alpha-LWO) parallel to [110](LAO), [010](alpha-LWO) parallel to [110](LAO) and [001](alpha-LWO) parallel to [001](LAO). Film cell parameters measured on a LaNiO3 buffer layer, setting as electrode for electric measurements, lead to a = 16.217(5) A, b = 5.607(1) A and c = 8.918(8) A. A Williamson-Hall plot carried out on a LWO film reveals that the microstrain is 0.16% along the growth direction while the coherent domain dimension is 16 nm. Piezoresponse force microscopy imaging and piezoloops recording demonstrate that these films are piezoelectric/ferroelectric on nanoscale. (C) 2016 Elsevier B.V. All rights reserved.