Abstract The adsorption of heptacene (7 A) on Cu(110) and Cu(110)-(2 × 1)-O was studied with scanning tunneling microscopy, photoemission orbital tomography and density functional calculations to reveal the influence of surface passivation on the molecular geometry and electronic states. We found that the charge transfer into the 7 A molecules on Cu(110) is completely suppressed for the oxygen-modified Cu surface. The molecules are aligned along the Cu-O rows and uncharged. They are tilted due to the geometry enforced by the substrate and the ability to maximize intermolecular π-π overlap, which leads to strong π-band dispersion. The HOMO-LUMO gap of these decoupled molecules is significantly larger than that reported on weakly interacting metal surfaces. Finally, the Cu-O stripe phase was used as a template for nanostructured molecular growth and to assess possible confinement effects.