The modification of the Au(111) Shockley-type surface state by an adsorbed monolayer of large π-conjugated molecules was investigated by high-resolution angle-resolved photoelectron spectroscopy (ARPES). We determined binding energy, band mass, and Rashba-splitting and discuss the results in the context of rare-gas adsorption on noble metals. This comparison allows the determination of the bonding strength of the adsorbates, found to be physisorptive with derived binding energies per molecule of 2.0eV for perylene-tetracarboxylic-dianhydride (PTCDA) and 1.5eV for naphtalene-tetracarboxylic-dianhydride (NTCDA). We will also present a superstructure model for the NTCDA/Au(111) system, deduced from low energy electron diffraction images (LEED) in combination with substrate band-backfolding.