We report the probe of specific triplet state properties of organic chromophores that are otherwise inaccessible in low viscous solution. The prototypical example demonstrated here is [Os(CO)(3)(Cl)(NDP)] (1) ((NDP)H = 2-naphthyl-7-dimethylanilino-1,3-propanedione), which, upon electronic excitation, undergoes intramolecular charge transfer in both S, and T, manifolds of NDP. The dipolar changes in S, and T, monitored via the solvatochromism for both fluorescence and phosphorescence were deduced to be 18.0 and 11.9 D, respectively. The appreciable difference in the dipolar change can be qualitatively rationalized by different extents of charge-transfer character between S, and T, states. The results led to the probe of other reactions in triplet manifold feasible.