Polarization-dependent X-ray absorption spectroscopy (XAS) offers an optimal method for studying the adsorption geometry of molecular adsorbates. For the planar TMPcs having D4h symmetry, both C1s-* or N1s-* excitations are suitable for determining molecular orientation. If the electric field vector of the incoming light is oriented parallel to the atomic pz wave functions forming the molecular π* orbital (i.e. out of the molecular plane), the absorption is maximal, whereas the transition is forbidden in the case of a perpendicular orientation. However, in our case the analysis of both C K and N K edge absorption spectra is hindered by the overlap with features from the MoS2 substrate and common carbon contaminations. An example for an N K edge spectrum in superposition with Mo M3,2 is shown in Figure (supporting information). However, also Co L edge XAS spectra show a pronounced angular dependence (see, e.g. Refs. ). They are determined to a large extent by multiplet effects due to the strong overlap between core level and valence wave functions. Nevertheless, in-plane and out-of-plane transitions can be distinguished (for details we refer to the literature, e.g. Refs. ). In the following, we will use the shape of the Co L3 XAS spectra for the estimation of the molecular orientation. We note that the shape of these spectra is almost independent on the fluorination of CoPc (cf., e.g. Refs ).