The molecular structure of thin pentacene film grown on a Cu(119) surface has been studied by near-edge X-ray absorption fine structure spectroscopy and scanning tunneling microscopy. The interaction between the π-molecular orbitals delocalized on the aromatic rings and the underlying copper substrate was deduced from XAS spectra. Pentacene molecules arrange with the main axis almost parallel with the Cu terraces according to the measured polarization dependence of the C 1s absorption spectra. For thickness exceeding 4 nm an upright arrangement of the molecules was observed with a dense herringbone-like ordering. The present study thus demonstrates that highly ordered pentacene films can be obtained on a Cu(119) vicinal surface both in a flat orientation for low coverages and in a bulk-like herringbone orientation for higher coverages.