Photodissociation dynamics of CF3Br has been investigated at 225 nm, where the (3)Q(0) state is accessed exclusively. It has been revealed that the ground state Br(P-2(3/2)) is hardly formed with a relative quantum yield less than 5%. The recoil anisotropy of Br *((2)p(1/2)) has been found to have a limiting value, beta(Br*) = 1.90 +/- 0.05. The total translational energy distribution for the Br* channel was well fitted by a Gaussian function with an average of 155 kJ/mol and a width of 30 KJ/mol. It has been proposed that the (3)Q(0) state is not bent and the dissociation on this surface proceeds in a collinear geometry. (C) 2007 Elsevier B.V. All rights reserved.