•First developed a three-phase coupled model of desulfurization in ESR process.•The MHD thermal flow in the reactor was clarified.•Distributions of sulfur concentration in the three phases were demonstrated.•An experiment was carried out to validate the simulation. A three-phase comprehensive mathematical model has been established to study the desulfurization behavior in electroslag remelting (ESR) process. The solutions of the mass, momentum, energy, and species conservation equations were simultaneously calculated by the finite volume method. The Joule heating and Lorentz force were fully coupled through solving the Maxwell’s equations with the assistance of the magnetic potential vector. The movements of the air-slag and slag-metal interfaces were described by the volume of fluid (VOF) approach. In order to include the influences of the air, the slag and the electric current on the desulfurization, a thermodynamic and kinetic module was introduced. An experiment was conducted to validate the model. The completely comparison between the measured and simulated data indicates that the model can describe the desulfurization behavior in the ESR process with an acceptable accuracy. The sulfur in the metal would be transferred into the slag under the combined effect of the slag treatment and the electrochemical reaction, and is primarily achieved in the period of the droplet formation. The sulfur in the slag then could be transferred into the air because of the oxidation. The maximum calculated removal ratio in the whole process is around 88%.