Mössbauer spectroscopy has been applied to study the structure and magnetostriction interdependence of metall/polymer composites with spatially oriented FeGa particles in a polymer matrix. Composites were synthesized combining modified polyurethane with nanocrystalline mechanosynthesized particles of magnetostrictive FeGa composition through polymerization to achieve a considerable magnetostrictive response. To increase magnetoelastic effects a spatial particle arrangement in the polymer matrix was generated. The magnetostrictive composition of the mechanosynthesized particles has been determined by Mössbauer spectroscopy, X-ray diffraction and TEM at different stages of ball milling. The microstructure of the composites via the particle orientation in the polymer has been researched by SEM and Conversion Mössbauer spectroscopy with the registration of resonant X-rays. The spatial particle inhomogeneity and magnetic anisotropy have been analyzed in order to reveal the factors determining the functional properties of the manufactured composites. Three-fold enhancement of the magnetostrictive response for FeGa/polyurethane composites with non-standard magnetic anisotropy has been demonstrated.