The incorporation of V into metastable cubic AlCrN coatings triggers the separation in a face-centered cubic (fcc) and a hexagonal wurtzite type phase whereas by using higher energetic growth conditions (ion energy), the metastable single-phase fcc structure can be retained. However, no preferential enrichment of V in either one of the phases was found by transmission electron microscopy. Independently from structural changes, the nitrides in all investigated coatings are in solid solution without any intermetallic compounds as it is shown by X-ray photoelectron spectroscopy, a detailed deconvolution of the measured core level spectra is presented. (C) 2007 Elsevier B.V. All rights reserved.