The local structure and the electronic properties of the active Ti sites in heterogeneous Ziegler–Natta catalysts, generated in situ by interaction of the precatalyst with different Al-alkyl activators, were investigated by combining X-ray absorption and valence-to-core X-ray emission spectroscopy (XAS and vtc-XES), coupled with UV/Vis, FTIR, and DFT theoretical calculations. Irrespective of the activator used, the active system was found to be a highly dispersed TiCl3-like phase in which the Ti sites are surrounded, not only by bridged chlorine ligands (with the same bond length of bulk TiCl3), but also by terminal chlorine ligands, at a much shorter distance. These results set Ziegler–Natta catalysts in the category of complex nanomaterials. Despite the observation that the investigated catalysts polymerize ethylene, cutting-edge XAS and XES techniques do not yet offer unequivocal proof for the presence of any alkyl chain attached to the Ti sites, as a consequence of the small fraction of the active sites.