Photoreaction of trans-2-[4′-(dimethylamino)styryl]benzothiazole (t-DMASBT) under direct irradiation has been investigated in dioxane, chloroform, methanol and glycerol to understand the mechanism of photoisomerization. Contrary to an earlier report, isomerization takes place in all these solvents including glycerol. The results show that restriction on photoisomerization leads to the increase in fluorescence quantum yield in glycerol. The results are consistent with the theoretically simulated potential energy surface reported earlier using time-dependent density functional theory (TDDFT) calculations. DFT calculations on cis isomers under isolated condition have suggested that cis-B conformer is more stable than cis-A conformer due to hydrogen-bonding interaction. In the ground state, cis-DMASBT is predominantly present as cis-B. The fluorescence spectra of the irradiated t-DMASBT suggested that photoisomerization follows not the adiabatic path as proposed by Saha et al., but the nonadiabatic path.