The mononuclear Mn(IV)-oxo complex [Mn-IV(O)(N4py)](2+), where N4py is the pentadentate ligand N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine, has been proposed to attack C-H bonds by an excited-state reactivity pattern [Cho, K-B.; Shaik, S.; Nam, W. J. Phys. Chem. Lett. 2012, 3, 2851-2856 (DOI: 10.1021/jz301241z)]. In this model, a E-4 excited state is utilized to provide a lower energy barrier for hydrogen-atom transfer. This proposal is intriguing, as it offers both a rationale for the relatively high hydrogen-atom-transfer reactivity of [Mn-IV(O)(N4py)](2+) and a guideline for creating more reactive complexes through ligand modification. Here we employ a combination of electronic absorption and variable-temperature magnetic circular dichroism (MCD) spectroscopy to experimentally evaluate this excited-state reactivity model. Using these spectroscopic methods, in conjunction with time-dependent density functional theory (TD-DFT) and complete-active space self-consistent field calculations (CASSCF), we define the ligand-field and charge-transfer excited states of [Mn-IV(O)(N4py)](2+). Through a graphical analysis of the signs of the experimental C-term MCD signals, we unambiguously assign a low-energy MCD feature of [Mn-IV(O)(N4py)](2+) as the E-4 excited state predicted to be involved in hydrogen-atom-transfer reactivity. The CASSCF calculations predict enhanced Mn-III-oxyl character on the excited-state E-4 surface, consistent with previous DFT calculations. Potential-energy surfaces, developed using the CASSCF methods, are used to determine how the energies and wave functions of the ground and excited states evolved as a function of Mn=O distance. The unique insights into ground- and excited-state electronic structure offered by these spectroscopic and computational studies are harmonized with a thermodynamic model of hydrogen-atom-transfer reactivity, which predicts a correlation between transition-state barriers and driving force.