Cl atoms in both ground [Cl(²P_3/2)] and excited spin orbit states [Cl*(²P_1/2)] were detected as photodissociation products of tetrachlorocyclopropene (TCCP) at 235 nm by Resonance Enhanced Multiphoton Ionisation – Time of Flight (REMPI-TOF) technique. From the experimental REMPI-TOF profile, the anisotropy parameter (β) for both the channels was found to be nearly zero. TOF profiles of both the Cl and Cl* channels could be fitted into single component translational energy distributions, with average energy of 7.7 and 8.6 kcal mol^-1 respectively. Time Dependent – Density Functional Theory (TDDFT) calculations using mpw1pw91/aug-cc-pVTZ level of theory suggested that, near 235 nm, the initially excited n_Cl-π*  state of TCCP may cross over to the nearby dissociative states, from where Cl/Cl* can be formed directly. Otherwise, the excited molecules may relax rapidly to the ground state, where the lowest energy dissociation channel is the C—C bond cleavage (ΔH=30.4 kcal mol^-1), as C—Cl bond breaking channels need high energy (ΔH=73.7 kcal mol^-1 and 85.5 kcal mol^-1). The biradical product of C—C bond breaking may rearrange to tetrachloroallene molecule with four equivalent C—Cl bonds, which can subsequently undergo C—Cl bond dissociation to produce Cl/Cl* atoms.