An investigation of the structure of several amorphous silicon (a-Si) films is presented. Samples were prepared by using the ion beam sputtering technique at different substrate deposition temperatures. X-ray absorption spectroscopy and multiple scattering formalism have been used to detect structural variations of the a-Si films. The analysis of the XANES (X-ray absorption near-edge structure) spectra shows that increasing the substrate deposition temperature leads to a structural change toward a higher-level short-range order.