The time-resolved and vibrational emission-resolved laser-induced fluorescence (LIF) spectra of jet-cooled supersonic diatomic sulfur molecule S2 have been studied in the range of 30 400~34 400 cm-1, and 184 bands were observed with high (0.1 cm-1) and low (0.3 cm-1) resolutions. 84 vibrational transitions were assigned to the Ｂ　３Σ－ｕ－Ｘ　３Σ－ｇ and Ｂ″　３Πｕ－Ｘ　３Σ－ｇ, and the molecular constants in the excited states Ｂ　３Σ－ｕ　ν=0～9 and Ｂ″　３Πｕ ν=2～12, including rotational constants, spin-orbit coupling constants, spin-rotation coupling constants, and spin-spin coupling constants, were obtained. The equilibrium molecular geometry in the vibronic ground state of Ｂ　３Σ－ｕ was determined by high-resolution spectrum. As there is perturbation between the Ｂ　３Σ－ｕ and Ｂ″　３Πｕ states of S2 molecule, the vibrational level intervals, spin-spin coupling constants and spin-orbit coupling constants of Ｂ　３Σ－ｕ and Ｂ″　３Πｕ states are anomalous variation, as well as the intensity of rotational transition and the transition selection rules. The anomalous behavior of the rovibrational spectra was qualitatively explained by the homogeneous perturbations between ３Σ－３Π states.