Unveiling the nature and the distribution of surface sites in heterogeneous catalysts, and for the Phillips catalyst (CrO3/SiO2) in particular, is still a grand challenge despite more than 60 years of research. Commonly used references in Cr K-edge XANES spectral analysis rely on bulk materials (Cr-foil, Cr2O3) or molecules (CrCl3) that significantly differ from actual surface sites. In this work, we built a library of Cr K-edge XANES spectra for a series of tailored molecular Cr complexes, varying in oxidation state, local coordination environment, and ligand strength. Quantitative analysis of the pre-edge region revealed the origin of the pre-edge shape and intensity distribution. In particular, the characteristic pre-edge splitting observed for Cr(III) and Cr(IV) molecular complexes is directly related to the electronic exchange interactions in the frontier orbitals (spin-up and -down transitions). The series of experimental references was extended by theoretical spectra for potential active site structures and used for training the Extra Trees machine learning algorithm. The most informative features of the spectra (descriptors) were selected for the prediction of Cr oxidation states, mean interatomic distances in the first coordination sphere, and type of ligands. This set of descriptors was applied to uncover the site distribution in the Phillips catalyst at three different stages of the process. The freshly calcined catalyst consists of mainly Cr(VI) sites. The CO-exposed catalyst contains mainly Cr(II) silicates with a minor fraction of Cr(III) sites. The Phillips catalyst exposed to ethylene contains mainly highly coordinated Cr(III) silicates along with unreduced Cr(VI) sites.