Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at the C K-edge has been used to investigate the orientation of benzene and phenoxy on the Zn-terminated basal face of ZnO. From these results, we deduce that benzene is oriented more or less parallel to the surface, bonding through its pi orbitals, whereas the phenoxy formed on exposure to phenol is bonded through O atop Zn. Benzene has an apparent tilt angle of the ring plane with respect to the surface of 11 +/- 5 degrees, whereas exposure to phenol results in a tilt angle of 35 +/-50. These tilt angles are similar to those obtained after adsorption on metal surfaces. The data are consistent with a stabilization mechanism of this polar surface which does not involve a substantial reconstruction.