We present X-ray reflectivity investigations of the concentration distribution in binary liquid thin films on silicon substrates. The liquid-vapor coexistence of the binary mixture investigated, hexane and perfluorohexane, is far from criticality. Therefore, a sharp interface separates the liquid film from the vapor. The data reveal a separation of the film in layers parallel to the substrate. A phase diagram is constructed as a projection to the (composition difference, temperature) space, covering a temperature range corresponding to the one-phase and the two-phase regime of the bulk liquid. Although the composition data indicate a mixing gap similar to that of the bulk system, there are two major differences: i) only the near-surface phase changes its composition significantly, and ii) a composition gradient in the film exists also at higher temperatures where in the bulk system the one-phase regime exists.