Phenol can serve as a model for examining the deactivation of the aromatic amino acid tyrosine following UV excitation, which mainly occurs through a repulsive πσ∗ state along the O-H bond. The reaction barrier formed by the conical intersection between the optically bright S1 (ππ∗) state and the dissociative S2 (πσ∗) state does not inhibit O-H bond rupture even though the excitation energy is below the barrier height. To examine the O-H bond-rupture dynamics in association with the initial excited vibrational modes, we used a picosecond laser to investigate the vibrational-mode-dependent excited-state lifetime of phenol under the S1/S2 conical intersection. Unexpectedly short lifetimes were observed in the S1 state for a″ symmetric vibrational modes (including v4, v16a, τOH, and v5). These results clarify recent theoretical calculations showing that the relaxation from S1 to S2 either occurs via symmetry-allowed non-adiabatic transitions or is topographically linked to a lower energy minimum on the multidimensional potential energy surface.