On photoexcitation at 193 nm, the ¹(π, π*) excited 1,4-pentadien-3-ol appears to be undergoing rapid internal conversion producing a highly energized ground electronic state, which is followed by dissociation to CH₂=CH-CH-CH=CH₂ (pentadienyl) and OH radicals as primary products. While the laser-induced fluorescence (LIF) showed that only 1.1% of the nascent OH (X²Π) are produced in the vibrationally excited state with V =1, there is no OH produced with V = 2. The rotational state distribution of OH is found to fit a Boltzmann distribution, characterized by a rotational temperature, T_rot, of 1250 = 100 K for the V = 0 and T_rot of 1020 ± 100 K for the V = 1 vibrational states. By measuring the Doppler spectroscopy of the V = 0 and V = 1 states of OH, an average relative translational energy of the photofragments is found to be 41.8 ± 5.0 and 37.4 ± 5.0 kJ mol-1, respectively. The real time formation of OH shows a dissociation rate constant of the 1,4-pentadien-3-ol to be (2.0 ± 0.4) 10⁷ s^-1. The above dissociation rate in relation to statistical Rice-Ramsperger-Kassel - Marcus (RRKM) theory suggests a resonance stabilization energy of the pentadienyl radical to be 70 kJ mol^-1.