AbstractThe recently reported luminescent chromium(III) complex 1³⁺ ([Cr(ddpd)₂]³⁺; ddpd=N,N′‐dimethyl‐N,N′‐dipyridine‐2‐yl‐pyridine‐2,6‐diamine) shows exceptionally strong near‐IR emission at 775 nm in water under ambient conditions (Φ=11 %) with a microsecond lifetime as the ligand design in 1³⁺ effectively eliminates non‐radiative decay pathways, such as photosubstitution, back‐intersystem crossing, and trigonal twists. In the absence of energy acceptors, such as dioxygen, the remaining decay pathways are energy transfer to high energy solvent and ligand oscillators, namely OH and CH stretching vibrations. Selective deuteration of the solvents and the ddpd ligands probes the efficiency of these oscillators in the excited state deactivation. Addressing these energy‐transfer pathways in the first and second coordination sphere furnishes a record 30 % quantum yield and a 2.3 millisecond lifetime for a metal complex with an earth‐abundant metal ion in solution at room temperature.