In one-color REMPI-TOF experiment, the photodissociation dynamics of POCl₃ has been studied by photolyzing POCl₃ and probing the chlorine atom photofragments, namely, Cl(²P_3/2) and Cl⁄(²P_1/2) using 2 + 1 REMPI scheme, in the 234–236 nm 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 ± 1.5 kcal/mol, while, for the slow components, the average translational energies are 1.5 ± 1.0 and 2.5 ± 1.0 kcal/mol, respectively. Apart from the chlorine atom elimination channel, Cl₂ elimination is also observed in the photodissociation of POCl₃.