Analysis of extended X-ray absorption fine structure (EXAFS) data for the MnIV -oxo complexes [MnIV (O)(DMM N4py)]2+ , [MnIV (O)(2pyN2B)]2+ , and [MnIV (O)(2pyN2Q)]2+ (DMM N4py=N,N-bis(4-methoxy-3,5-dimethyl-2-pyridylmethyl)-N-bis(2-pyridyl)methylamine; 2pyN2B=(N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine, and 2pyN2Q=N,N-bis(2-pyridyl)-N,N-bis(2-quinolylmethyl)methanamine) afforded Mn=O and Mn-N bond lengths. The Mn=O distances for [MnIV (O)(DMM N4py)]2+ and [MnIV (O)(2pyN2B)]2+ are 1.72 and 1.70 Å, respectively. In contrast, the Mn=O distance for [MnIV (O)(2pyN2Q)]2+ was significantly longer (1.76 Å). We attribute this long distance to sample heterogeneity, which is reasonable given the reduced stability of [MnIV (O)(2pyN2Q)]2+ . The Mn=O distances for [MnIV (O)(DMM N4py)]2+ and [MnIV (O)(2pyN2B)]2+ could only be well-reproduced using DFT-derived models that included strong hydrogen-bonds between second-sphere solvent 2,2,2-trifluoroethanol molecules and the oxo ligand. These results suggest an important role for the 2,2,2-trifluoroethanol solvent in stabilizing MnIV -oxo adducts. The DFT methods were extended to investigate the structure of the putative [MnIV (O)(N4py)]2+ ⋅(HOTf)2 adduct. These computations suggest that a MnIV -hydroxo species is most consistent with the available experimental data.