In this work the capability of the proton induced X-ray emission (PIXE) technique to monitor a rapid, non-destructive and accurate quantification of Al on and in Si-based matrix is discussed. Optimization of PIXE acquisition parameters was performed using as reference a thin Al film (2.5 nm) thermally evaporated onto silicon substrate. In order to improve the sensitivity for Al detection and quantitative determination, a systematic study was undertaken using proton ion beam at different energies (from 0.3 to 3 MeV) with a different tilting angle (0°, 60°, and 80°). The limit of detection (LOD) was found to be lower than 0.2 nm. The optimum PIXE conditions (energy, angle) were applied for determining the Al doping concentration in thin (1 µm) 4H-SiC homoepitaxial layer. The Al concentration as determined by PIXE was found to be 3.9x1020 at/cm3 in good agreement with SIMS measurements, and the LOD was estimated to be 6x1018 at/cm3.