The formation of a series of Xe−CuEtioI [Cu(II) etioporphyrin I] complexes on Cu(001) surfacewas identified by scanning tunneling microscopy (STM) at cryogenic condition. The binding sites of xenonto CuEtioI molecule were directly revealed by high-resolution STM images in combination with controlledmanipulation. The interaction between xenon atoms and CuEtioI in the on-top configuration is suggestiveof a charge-induced dipole interaction. The structural parameters obtained with the STM complement resultsfrom spectroscopic studies of van der Waals complexes.