Photodissociation of jet-cooled thiomethoxy radical (CH3S) via the (A) over tilde (2)A(1) <- (X) over tilde E-2(3/2) transition is studied in the region of 344-362 nm. The H-atom product channel is directly observed by H-atom photofragment yield spectrum and photofragment translational spectroscopy. Two vibronic levels of (A) over tilde (2)A(1), 2(1)3(1) and 2(1)3(2), dissociate to H + H2CS, while the others in the vicinity (2(1)3(3) and 3(n), n = 3-6) dissociate to CH3 + S(P-3(J)) (based on a previous study by Neumark and co-workers). The H + H2CS product translational energy release is not repulsive and peaks at similar to 9 kcal/mol; the H-atom angular distribution is isotropic. The dissociation mechanism is consistent with internal conversion of the excited (A) over tilde (2)A(1) to the ground state (X) over tilde E-2 followed by unimolecular dissociation of E-2. (C) 2008 Elsevier B.V. All rights reserved.