Vacuum ultraviolet (VUV) photodissociation of jet-cooled SH radical is studied at the photolysis wavelength of 121.6 nm using high-n Rydberg atom time-of-flight (HRTOF) technique. Both the ground-state S(P-3(J)) and the excited-state S(D-1(2)) and S(S-1(0)) products are observed, with a branching fraction of S(P-3(J)): S(D-1(2)):S(S-1(0)) = 0.07 +/-0.01:0.82 +/- 0.01:0.11 +/- 0.01. The spin-orbit branching fraction of the minor S(P-3(J)) product is S(P-3(2)):S(P-3(1)):S(P-3(0)) = 0.28 +/-0.12:0.54 +/- 0.16:0.18 +/- 0.09. The predominant production of S(D-1(2)) is consistent with a direct dissociation from the repulsive 2(2)Pi state. The S(P-3(J)) product fine-structure state distribution from SH photodissociation at 121.6 nm is significantly different from that in the UN region. (c) 2005 Elsevier B.V. All rights reserved.