Trans and cis conformers of 3-methylthioanisole have been spectroscopically investigated to reveal the conformer specific structural changes upon the S1(ππ*)-S0 excitation. The conformational cooling during the supersonic expansion is found to be quite efficient in the Ar carrier gas giving the trans conformational isomer exclusively in the molecular beam, whereas both trans and cis conformers are populated in the jet when the sample is carried in Ne. Using the Stark deflector, trans and cis conformers are unambiguously identified, showing the distinct Stark deflection profiles according to their sufficiently different dipole moments of 1.013 or 1.670 D, respectively. For the trans conformer, the methyl moiety on the meta-position adopting the eclipsed geometry in S0 transforms into the staggered geometry in S1 to activate a series of the CH3 torsional mode. A Hamiltonian with the one-dimensional sinusoidal torsional potential is solved using the free-rotor basis set to explain the experiment, giving the 3-fold torsional barrier of 34 and 304 cm-1 for S0 and S1, respectively. For the cis conformer, on the other hand, the CH3 torsion is little activated in the S1-S0 transition as both S0 and S1 adopt the staggered geometry at the minimum energy points. The doublet of each band of the cis conformer is ascribed to tunneling split due to the very low CH3 torsional barrier of 27 cm-1 in S0. It is found that the cis conformer undergoes a planar to pseudoplanar structural change upon the S1-S0 transition. Theoretical calculation based on the double-well model potential curve could explain the experiment quite well, suggesting that the SCH3 moiety of the cis conformer in S1 becomes out-of-plane with respect to the plane of the phenyl moiety. This implies that excited-state predissociation dynamics of trans and cis conformers of the title molecule might be different.