We have investigated the local electronic structure of n-octane adsorbed on the Cu(110) surface using symmetry-resolved x-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) in combination with density functional theory (DFT) spectrum calculations. We found new adsorption-induced states in the XE spectra, which we assign to interaction between the bonding CH orbitals and the metal surface. By performing a systematic investigation of the influence of different structural parameters on the XA and XE spectra, we conclude that the molecular geometry is significantly distorted relative to the gas-phase structure. The bonding to the surface leads to a strengthening of the carbon–carbon bonds and a weakening of the carbon–hydrogen bonds, consistent with a rehybridization of the carbons from sp3 to sp2.8.