Iron photosensitizers represent a holy grail in photochemistry, but their widespread implementation is limited by their short excited-state lifetimes and poor cage escape yields. Here, the introduction of an anthracene moiety appended to an iron(III) complex allowed to solve both limitations and generate a novel dyad exhibiting an extraordinary excited-state lifetime of 11.5 μs. The key to achieving this remarkably long lifetime is the depopulation of the short-lived iron-centered emissive excited state to populate a dark triplet state located on the anthracene-like moiety with a spin-forbidden deactivation. Population of the triplet anthracene only occurs with ∼10% efficiency in acetonitrile but still allows expansion of the scope of reactivity accessible with iron-based photosensitizers, which now encompasses energy transfer to