Developing　light-harvesting　materials　with　broad　spectral　response　is　of　fundamental　importance　in　full-spectrum　solar　energy　conversion.　We　found　that,　when　a　series　of　earth-abundant　metal　(Cu,　Co,　Ni　and　Fe)　salts　are　dissolved　in　coordinating　solvents　uniformly　dispersed　nanodots　(NDs)　are　formed　rather　than　fully　dissolving　as　molecular　species.　The　previously　unrecognized　formation　of　this　condensed　state　is　ascribed　to　spontaneous　aggregation　of　molecular　transition-metal-complexes　(TMCs)　via　weak　intermolecular　interactions,　which　results　in　redshifted　and　broadened　absorption　into　the　NIR　region　(200–1100　nm).　Typical　photoredox　reactions,　such　as　carbonylation　and　oxidative　dehydrogenation,　well　demonstrate　the　feasibility　of　efficient　utilization　of　NIR　light　(λ＞780　nm)　by　TMCs　NDs.　Our　finding　provides　a　conceptually　new　strategy　for　extending　the　absorption　towards　low　energy　photons　in　solar　energy　harvesting　and　conversion　via　photoredox　transformations.　©　2022　Wiley-VCH　GmbH.