Sulphidic spent caustic (SSC) is an alkaline waste stream which is generated during caustic scrubbing of liquefied petroleum gas and ethylene products. Due to presence of high concentrations of sulphides and phenols, the waste stream requires proper treatment before mixing with the low strength wastewater streams produced from other refinery operations. Electrochemical process is an emerging treatment method that can work efficiently at ambient conditions. The present study reports performance of electro-Fenton (EF) process for the treatment of synthetic SSC wastewater (sulphides = 10 g L−1, phenol = 2 g L−1 and pH = 12.9). The EF runs were carried out for 2 h duration in a reactor equipped with iron electrodes. The effects of H2O2 dose (0.26–1.3 M), current density (1–20 mA cm−2), pH (4.5–12.9) and stirring speed (100–1000 rpm) were investigated on removal of pollutants. The H2O2 was rapidly consumed in initial 30 min during which the significant fraction of the pollutants was degraded or removed. The optimum conditions for EF process were found to be as follows: pH = 4.5, H2O2 dose = 1.05 M, current density = 5 mA cm−2 and stirring speed = 500 rpm. At these conditions, the maximum sulphide and phenol removals from the wastewater were 98% and 91%, respectively. The results will be helpful to the wastewater treatment plant operators worldwide dealing with high concentrations of such pollutants.