In one-color REMPI-TOF experiment, the photodissociation dynamics of POCl 3 has been studied by photolyzing POCl 3 and probing the chlorine atom photofragments, namely, Cl( 2 P 3/2 ) and Cl ∗ ( 2 P 1/2 ) using 2+1 REMPI scheme, in the 234–236nm region. We have determined the centre-of-mass photofragment speed distribution, recoil anisotropy parameter, and the spin–orbit branching ratio for chlorine atom elimination channels. The anisotropy parameters for Cl and Cl ∗ are the same, and characterized by a value of 0.0±0.05. Two components, namely, the fast and the slow, are observed in the translational energy distributions of Cl and Cl ∗ . The average translational energies for the Cl and Cl ∗ channels for the fast components are 12.5±1.5 and 16.8±1.5kcal/mol, while, for the slow components, the average translational energies are 1.5±1.0 and 2.5±1.0kcal/mol, respectively. Apart from the chlorine atom elimination channel, Cl 2 elimination is also observed in the photodissociation of POCl 3 .