Abstract We report on polarized X-ray absorption spectroscopy (P-XAS) study of La 0.7 Sr 0.3 MnO 3 (LSMO) films, epitaxially grown by laser ablation on tensile (SrTiO 3 ) and compressive (LaAlO 3 ) substrates. In-plane and out-of-plane bond information was obtained by setting the angle between electric field vector and film surface close to 0 and 90°, respectively. Measurements show significant modifications in the average MnO 6 octahedron around manganese atoms in the film plane for tensile and compressive substrates. The modifications of the XANES spectra were correlated to a modification in the average MnO distance and a distortion of the MnO 6 octahedra. Ab initio calculations using the full multiple scattering approach confirm the structural model of distorted octahedron.