Resonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ∼240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the C[Single_Bond]S antisymmetry stretch +C[Single_Bond]C==C bend mode ν21(B2) at 754 cm-1 and the H7C3[Single_Bond]C4H8 twist ν9(A2) at 906 cm-1, suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points 1B1/1A1 and 1B2/1A1 between 2 1A1 and 1 1B2 or 1 1B1 potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C[Single_Bond]S bonds and via the conical intersection point 1B1/1A1 was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point 1B2/1A1 was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface. [ABSTRACT FROM AUTHOR]