The electronic excited states reactivity of [Mn(im)(CO) 3 (phen)] + (phen = 1,10-phenanthroline; im = imidazole) ranging between 420 and 330 nm have been analyzed by means of relativistic spin-orbit time-dependent density functional theory and wavefunction approaches (state-average-complete-active-space self-consistent-field/multistate CAS second-order perturbation theory). Minimum energy conical intersection (MECI) structures and connecting pathways were explored using the artificial force induced reaction (AFIR) method. MECIs between the first and second singlet excited states (S 1 /S 2-MECIs) were searched by the single-component AFIR (SC-AFIR) algorithm combined with the gradient projection type optimizer. The structural, electronic, and excited states properties of [Mn(im) (CO) 3 (phen)] + are compared to those of the Re(I) analogue [Re(im)CO) 3 (phen)] +. The high density of excited states and the presence of low-lying metal-centered states that characterize the Mn complex add complexity to the photophysics and open various dissociative channels for both the CO and imidazole ligands.