On excitation at 193 nm, tetrahydrofuran (THF) generates OH as one of the photodissociation products. The nascent energy state distribution of the OH radical was measured employing laser induced fluorescence technique. It is observed that the OH radical is formed mostly in the ground vibrational level, with low rotational excitation (~3%). The rotational distribution of OH (v 9"=0, J) is characterized by rotational temperature of 1250 ± 140 K. Two spin-orbit states, ²II_3/2 and ²P _½ of OH are populated statistically. But, there is a preferential population in Λ doublet levels. For all rotational numbers, the ²II⁺(A) levels are preferred to the ²II⁻(A') levels. The relative translational energy associated with the photoproducts in the OH channel is calculated to be 17.4 ± 2.2 kcal mol−1, giving an f_T value of, ~36%, and the remaining 61% of the available energy is distributed in the internal modes of the other photofragment, i.e., C₄H₇. The observed distribution of the available energy agrees well with a hybrid model of energy partitioning, predicting an exit barrier of ≈16 kcal mol⁻¹. Based on both ab initio molecular orbital calculations and experimental results, a plausible mechanism for OH formation is proposed. The mechanism involves three steps, the C–O bond cleavage of the ring, H atom migration to the O atom, and the C–OH bond scission, in sequence, to generate OH from the ground electronic state of THF. Besides this high energy reaction channel, other photodissociation channels of THF have been identified by detecting the stable products, using Fourier transform infrared and gas chromatography.