Medium-energy ion spectroscopy (MEIS) has been used to study the depth profile and deduce the distribution of possible cationic substitutions in LaAlO3/SrTiO3 (LAO/STO) heterointerfaces. Analysis of La and Sr peaks in aligned and random MEIS spectra indicates that the surface layers of LAO on an STO substrate are not homogeneous and stoichiometric if the film thickness is less than 4 unit cell layers. This is possibly caused by a redistribution of La and Sr at the interface. Kelvin probe force microscopy reveals an inhomogeneous distribution of the surface potential in a 4 unit cell LAO film, indicating micrometer-sized regions of different compositions. Our findings provide a novel view on the microstructural origin of the electrically conductive interfaces.