Bridged μ-oxo iron bisporphyrins serve as photocatalysts for oxidative organic transformations, but suffer from low quantum efficiency. This low performance has been primarily attributed to the short lifetime of Fe(II)/Fe(IV)=O state formed after LMCT excitation, but a competing proposal claims that the majority photoproduct is a catalytically inactive ligand-centered ion pair. We use femtosecond optical and M_2,3-edge XANES spectroscopy to investigate the early photodynamics of the μ-oxo iron bisporphyrin, (TPPFe)₂O, providing evidence for the preferential formation of an TPPFe(III)⁺/TPPFe(III)-O^- ion pair state instead of the desired TPPFe(II)/TPPFe(IV)=O. This work provides new guidance for catalyst design, suggesting that the excited-state potential surfaces must be redesigned to promote formation of the catalytically active state.