Ti-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) provides a means for generating Ti(III) complexes by homolysis of the Ti-O bond. It has been determined that bis-Cp-Ti-TEMPO complexes readily undergo homolytic cleavage while the mono-Cp-Ti-TEMPO complexes do not. Here Ti K- and Cl K-edge XAS are applied to directly determine the oxidation state of TiCl3TEMPO, TiCpCl2TEMPO, and TiCp2ClTEMPO, with reference to Ti(III) and Ti(IV) complexes of known oxidation state. The Ti K- edge data show that Ti(III) complexes exhibit a pre-edge feature similar to 1 eV lower than any of the Ti(IV) complexes; while the Cl K- edges show that Ti(III) complexes have a Cl K- pre-edge feature to similar to 1 eV higher energy than any of the Ti(IV) complexes. Taken together, the Ti and Cl K- edge data indicate that the Ti-TEMPO complexes are best described as Ti(IV)-TEMPO anions (rather than Ti(III)-nitroxyl radicals). In addition, the Cl K- edges indicate that replacement of Cl by Cp weakens the bonding with the remaining ligands, with the Cl 3p covalency decreasing from 25% to 21% to 17% on going from TiCl3TEMPO to TiCpCl2TEMPO to TiCp2ClTEMPO. DFT calculations also show that the electronic structures of the Ti -TEMPO complexes are modulated by the replacement of chloride by Cp. The effect of the Cp on the ancillary ligation is one factor that contributes to facile Ti-O bond homolysis in TiCp2ClTEMPO. However, the results indicate the primary contribution to the energetics of Ti-O bond homolysis in TiCp2ClTEMPO is stabilization of the three-coordinate product by Cp.