Abstract: We present a first velocity map imaging study on the 234 nm photodissociation dynamics of two carbon-chain branched alkyl bromides, neopentyl bromide (denoted as NPB) and tert-pentyl bromide (denoted as TPB). Unlike the 234 nm photodissociation of the unbranched n-C5H11Br molecule where only a direct fission of the C-Br bond is involved, the branched NPB and TPB molecules exhibit one and two more independent dissociation pathways with much energy being decayed via an extensive excitation of the bending modes of the parent molecules prior to the C-Br bond fission. This observation strongly suggests that the disso-ciation coordinate for the two carbon-chain branched molecules is no longer solely ascribed to the C-Br stretching mode but rather a combination of the bending-stretching modes.