We report the electronic structure and the charge transport mechanism of highly ordered films of pentacene on Cu(110) surface studied by angle‐resolved ultraviolet photoemission spectroscopy using synchrotron radiation. For a flat‐lying monolayer film, we observed the evidences of (i) formation of the interface states and (ii) two‐dimensional intermolecular band dispersion of the resultant interface states, which may originate from the hybridization between the molecular orbi‐tals and the wave function of the substrate. For an upright‐standing multilayer film, we observed the two‐dimensional intermolecular band dispersion, which originates from the intermolecular π–π interaction. The observed effective masses of the hole for different azimuths demonstrate the presence of the anisotropy of the hole mobility in pentacene crystals also at higher temperatures. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)