VOCl3 and TiCl4 exhibit a similarity of various thermal properties, causing difficulty for these components separation through distillation technique. Dynamic behavior of distillation process of VOCl3-TiCl4 mixture was modeled based on the mass and energy balances, revealing in a model form of the ordinary differential equations. Influences of heating power, airflow, initial concentration, and operating pressure were considered. Simulation results show an ineffective distillation of the mixture under natural pressure. However, the reduction of the operating pressure advanced the pure TiCl4 recovery performance. Compared to experimental data, the relative error of the simulation findings is less than 5%, indicating the potential of the application of the proposed model for describing the distillation of the VOCl3-TiCl4 mixture.