The photodissociation Of n-C4H9W at 232-267 nm has been investigated utilizing velocity map ion imaging. The two-dimensional images provide detailed information on the translational energy distributions and anisotropy parameters of the photoprodnets (Br and Br*). The experimental data and our ab initio calculations indicate that the photodissociation in the investigated range originates from the three low-lying dissociative electronic states, as assigned as 1A", 2A' and 3A' in Cs symmetry. Then, the origins of the photofragments (Br and Br*) are assigned to the individual pathways. The dissociation energy of the C-Br bond of n-C4H9Br is determined to be D-0 = 333.4 +/- 1.5 kJ/mol. (c) 2005 Elsevier B.V. All rights reserved.