The active role of the optically dark pi sigma* state, following UV absorption, has been implicated in the photochemistry of a number of biomolecules. This work focuses on the role of the pi sigma* state in the photochemistry of phenol upon excitation at 200 nm. By probing the neutral hydrogen following UV excitation, we show that hydrogen elimination along the dissociative pi sigma* potential energy surface occurs within 103 30 fs, indicating efficient coupling at the S-1/S-2 and S-0/S-2 conical intersections, with no identifiable role of statistical unimolecular decay of vibronically excited (SO) phenol in the timeframe of our measurements.