We have shown that ion beams can be used to probe the surface composition and molecular orientation of liquid surfaces. Time-of-flight analysis of the kinetic energy of scattered inert gas ions and recoil atoms ejected from the surface reveals the identity of atoms in the topmost atomic surface layer of the liquid. In this report we describe the first scattering/recoil experiments on surfaces of a liquid siloxane and glycerol using helium, neon and argon ions in the 2-3 keV energy range. Analysis of peak intensities as a function of experimental parameters can be used to infer average molecular orientations in the surface. Spectra from the liquid siloxane are similar to that reported by Bertrand et al. [J. Phys. Chem. 97, 131 788 (1993)] for the long-chain hydrocarbon hexatriacontane deposited as oriented solid films on Si wafers. Our data indicates that the siloxane backbone is effectively shielded by the attached hydrocarbon groups, and for incoming ions the molecule effectively resembles a hydrocarbon. Recent sum-frequency generation spectroscopy experiments [J. Phys. Chem. B 101, 4607 (1997)] suggest that a glycerol molecule in the liquid is, on average, oriented with the carbon backbone normal to the surface. Our data is consistent with this:result, but scattering/recoiling simulations are needed to definitively determine the orientation. (C) 1997 American Institute of Physics.