We report the photodissociation dynamics of ortho-iodobenzyl chloride (o-C6H4I(CH2Cl)) in the ultraviolet. The gas phase dissociation dynamics of o-iodobenzyl chloride at 222, 236, 266, 280, and similar to304 nm was monitored by probing the quantum yields of V ((2)p(1/2)) as well as C1* (P-2(1/2)) production using suitable resonance enhanced multiphoton ionization detection schemes. We find that only iodine atoms in the ground (I (P-2(3/2))) as well as excited (1*) states are produced in the dissociation. No Cl (P-2(3/2)) or Cl* atoms were detected. This accidental bond selective dissociation in o-iodobenzyl chloride is perhaps due to weak coupling among various chromophores present in the molecule and inefficient interchromophore energy transfer among them. (C) 2004 Published by Elsevier B.V.