Measuring directly the composition, the distribution of constituents as function of the depth and the orientation of molecules at liquid surfaces is essential for determining physicochemical properties of liquid surfaces. While the experimental tools that have been developed for analyzing solid surfaces can in principal be applied to liquid surfaces, it turned out that they had to be adjusted to the particular challenges imposed by liquid samples, e.g. by the unavoidable vapor pressure and by the mobility of the constituting atoms/molecules. In the present work it is shown, how electron spectroscopy and ion scattering spectroscopy have been used for analyzing liquid surfaces. The emphasis of this review is on using the structural information gained for determining the physicochemical properties of liquid surfaces.