The photodissociation dynamics of benzoic acid monomer at 266 nm is investigated by probing the nascent OH photoproduct using the laser-induced-fluorescence (LIF) technique. The nascent OH radical is distributed in the ground vibrational state and the rotational temperature is 620 +/- 30 K. The F, ((2)Pi(3/2)) and F-2 ((2)Pi(1/2)) spin-orbit states of OH photofragment are unstatistically populated, and Lambda-doublet levels are not equally populated. The present study associated with the available dynamics information predicts that OH radical is mainly produced from benzoic acid monomer on the T-2 energy surface. (c) 2007 Elsevier B.V. All rights reserved.