The adsorption of lead phthalocyanine (PbPc) on the hydrogen passivated Ge(001)‐2×1 surface is investigated by photoelectron spectroscopy, scanning tunnelling microscopy and near‐edge absorption fine structure (NEXAFS) techniques. The substrate‐molecule interaction is observed to be weak, with the molecule‐molecule interaction predominantly determining the ordering at the interface. The molecules in the first observable islands adopt a crystal structure similar to the bulk triclinic structure, with the stacking axis parallel to the substrate. Adlayers are ∼0.8 nm in height and the average tilt in thicker layers, as determined by NEXAFS, is consistent with this crystal structure. However, the first island height observed is ∼1.6 nm, which is considered to be a bilayer of PbPc molecules; the average tilt in these initial layers is slightly larger. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)