The intramolecular vibrational energy redistribution (IVR) of the OH stretching vibration of jet-cooled phenol-h₆ (C₆H₅OH) and phenol-d₅ (C₆D₅OH) in the electronic ground state has been investigated by picosecond time-resolved IR-UV pump-probe spectroscopy. The OH stretching vibration of phenol was excited with a picosecond IR laser pulse, and the subsequent temporal evolutions of the initially excited level and the redistributed ones due to the IVR were observed by multiphoton ionization detection with a picosecond UV pulse. The IVR lifetime for the OH stretch vibration of phenol-h₆ was determined to be 14 ps, while that of the OH stretch for phenol-d₅ was found to be 80 ps. This remarkable change of the IVR rate constant upon the dueteration of the CH groups strongly suggests that the “doorway states” for the IVR from the OH level would be the vibrational states involving the CH stretching modes. We also investigated the IVR rate of the CH stretching vibration for phenol-h₆. It was found that the IVR lifetime of the CH stretch less than 5 ps. The fast IVR is described by the strong anharmonic resonance of the CH stretch with many other conbinations or overtone bands.