Solvents are known to affect the triplet state structure and reactivity. In this paper, we have employed time-resolved resonance Raman (TR3) spectroscopy to understand solvent-induced subtle structural changes in the lowest excited triplet state of thioxanthone. Density functional theory (DFT) combined with the self-consistent reaction field (SCRF) implicit solvation model has been used to calculate the vibrational frequencies in the solvents. Here, we report a unique observation of the coexistence of two triplets, which has been substantiated by the probe wavelength-dependent Raman experiments. The coexistence of two triplets has been further supported by photoreduction experiments carried out at various temperatures.