A comparative study of the photophysical properties of selected, 7-(diethylamino)coumarins, with different electron-withdrawing substituents at 3-position (dye I, II, and III) has been made in various aprotic solvents. It is found that the absorption and fluorescence characteristics of the dyes are strongly dependent on both the substitution at the 3-position and also on the properties of the solvents used. These observations are discussed in terms of the formation and stabilization of the twisted intramolecular charge transfer (TICT) state that determines the probability of prospective lasing action from the dyes. In the process, an effective laser dye (dye III), in which the TICT state does not act as intramolecular fluorescent quencher has been identified.