Direct (UV) and hydrogen peroxide-assisted (UV/H2O2) photolysis were investigated in bench-scale for removing the organic compounds present in the electrodialysis reversal (EDR) brine from a refinery wastewater reclamation plant. In the UV/H2O2 experiments, a COD:H2O2 molar ratios of 1:1, 1:2 and 1:3 were tested by recirculating the brine in the UV reactor for 120 min. Results showed a significant reduction in UVA254, whereas no reduction was observed for chemical oxygen demand (COD), in the UV process, suggesting great cleavage but limited mineralization of the organic matter. UV/H2O2 with C:H2O2 ratio of 1:3 exhibited high efficiency in removing the organic matter (COD removal of 92% with an electrical energy per removal order (EEO) value of 22 kW h m-3). Although the EDR brine has high salinity, no strong scavenging effect of •OH was found in the water matrix due to the high concentration of anions, especially chloride and bicarbonate. Finally, UV/H2O2 with C:H2O2 ratio of 1:3 and residence time of 120 min is an efficient alternative for organic matter removal of EDR brine from refinery wastewater reclamation plant showing total capital cost (CapEx) estimated at US$ 369,653.00 and total operational cost (OpEx), at US$ 1.772 per cubic meter of effluent.