ABSTRACT This study aimed to apply aquathermolysis technology to remove thiophene sulfur in vacuum residue to obtain qualified petroleum coke products based on a well-designed Fe-Zr-Al catalyst. A coprecipitation method was first developed to synthesize Fe-Zr-Al composite metal oxide catalyst. The thiophene model oil was selected as the reaction system to investigate the process conditions. By adding surfactants into the reaction system to strengthen the mass transfer process of oil–water two-phase, the desulfurization rate of aquathermolysis was improved. It was shown in this study that under the conditions of oil–water ratio of 3:7, temperature of 280°C, pressure of 4 MPa and reaction duration of 60 h, the desulfurization rate could reach 44.39%. The further introduction of 2.4% Sorbitan oleate into the above reaction system could significantly enhance the desulfurization rate to 60.20%. Under the action of Fe2O3 lattice oxygen, thiophene was oxidized and C-S bond was broken, so as to achieve the purpose of desulfurization. The decomposition of water generated active oxygen to continuously replenish lattice oxygen of Fe2O3. The current founding can provide a new way for the effective desulfurization of vacuum residue to produce qualified petroleum coke products.