Surface crossing of bound (S1, ππ*) and continuum (S2, πσ*) states has been observed in the ultrafast S–D bond dissociation reaction of thiophenol-d1. It is manifested by an unanticipated variation of fragment angular distribution as a function of the excitation energy. The anisotropy parameter (β) of +0.25 at the S1 origin decreases to −0.60 at ∼600 cm–1 above the S1 zero-point level, giving a broad peak in β with a bandwidth of ∼200 cm–1. The peak in β is ascribed to the in-plane S-D bending mode excitation by which the nuclear configuration in the proximity of the S1/S2 conical intersection seam is directly accessed, showing a mixed character of parallel (S1–S0) and perpendicular (S2–S0) transition dipole moments at the same time. As a result, the dynamic aspect of the conical intersection is experimentally revealed here through direct access to the nuclear configuration on the multidimensional conical intersection seam.