Quaternary GaInAsSb films alloys were grown by MOVPE technique on GaSb substrates with different growth conditions such as substrate orientation and thickness. The composition of the films determines their bandgap, and also how well they are lattice matched to the substrate. It is thus essential to determine it accurately, which is not a trivial task in this system. The composition of the samples was studied with a combination of Particle Induced X-ray Emission (PIXE) and Rutherford Backscattering Spectrometry (RBS) experiments. The RBS experiments were done with a 2 MeV He-4(+) or H+ ion beam, according to the thickness of the films, and were used to determine the thickness of the samples. The PIXE experiments were performed at grazing angle conditions and provided accurate elemental composition information. It was found that for thin layers (300 nm) there is a dependence of In incorporation into the matrix according to the substrate orientation, although this tendency was not found for thicker films (2 mu m).