The triphenylamine-thiadiazole molecule (TPA-NZP) is a newly popular, highly efficient OLED fluorescent emitter with exciton utilization efficiency exceeding the upper limit of spin statistics (25%). In this work, the optical spectra and the radiative and nonradiative decay rate constants have been investigated theoretically for TPA-NZP in hexane, ethyl ether, tetrahydrofuran, and dimethylformamide solvents, in comparison with the gas phase. We observed the evolutions of the excited states from the hybridized local and charge-transfer (HLCT) character to complete intramolecular charge transfer (CT) character with the increase of the solvent polarities. It is found that upon increasing the solvent polarity, the amount of red shift in the absorption peak is much less than that of emission, resulting in breakdown of the mirror symmetry. This is because that 0-0 transition energy is red-shifted but the vibrational relaxation increases with the solvent polarity, leading to subtraction in absorption while addition in emission. The radiative decay rate constant is calculated to be almost independent of polarity. The nonradiative decay rate increases by almost one order of magnitude from that in nonpolar hexane to the strongly polarized dimethylformamide, which is attributed to the dual effects of the red shift in the gap and enhancement of the vibrational relaxation by solvent polarity.