We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. it is found that O-2 and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O-2 at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between An and pentacene by 0.25 eV, presumably due to a modification of the An surface properties.</p