The environmentally friendly insulating gas CF3I is a promising replacement for SF6 due to its excellent insulation and arc extinguishing performance. In the arc chamber of high-voltage circuit breakers filled with CF3I/CO2, the near-electrode sheath dominates the current transfer process between contact and arc column during arc formation, which has a significant effect on the transition from glow to arc discharge. The 30%CF3I/70%CO2 was taken as the research object in this research, and a more perfect fluid model was established considering the influence of diffusion current. The arc formation process between the contacts at the preliminary stage of circuit breaker interruption was conducted. The results show that the arc formation process can be divided into three stages: glow discharge, abnormal glow discharge, and arc discharge. As the arc formation process proceeds, the thickness of the near-cathode sheath decreases gradually. When the arc reaches stability with the current density 8×106–1.6×107A·m−2, the thickness of the near-cathode sheath is 7 μm, the steep voltage fall near the cathode sheath is generated within 7 μm away from the cathode surface, and this voltage fall almost does not change with the current density. CF3I− is the dominant negative ion between the contacts, which indicates that CF3I has excellent electron adsorption performance and is beneficial to arc deionization. The computational results of this work were compared with the existing experimental ones, which shows that the model used in this work is accurate enough. Finally, suggestions for model optimization and future work are given.