In this work, a pseudo-2D model including electrode reaction and membrane separation of the high-temperature electrochemical hydrogen pump (HT-EHP) was proposed to separate a CO-containing hydrogen mixture. Rigorous kinetics of electrochemical reaction and competitive adsorption was introduced to reach accurate performance prediction. The simulated polarization curves of three different feed gases, namely, no-CO and narrow and wide CO content ranges, at different temperatures were consistent with the experimental data (R 2 ≥ 0.90). Compared to previous work, the accuracy of the developed pseudo-2D model has been improved by 78.8% and 62.2%, respectively, under two feedstock conditions. Quantitative analysis of current density and catalyst coverage was achieved under various process conditions, demonstrating the applicability of HT-EHP pseudo-2D model. Feasible suggestions for the optimization design of HT-EHP were provided by analyzing the relationship between equipment scale, feed flow rate, current density and hydrogen recovery rate. Thus, the developed pseudo-2D model can be beneficial in the design and optimization of the HT-EHP system, and HT-EHP as an efficient membrane based technology is promising for the separation of CO-containing hydrogen mixtures in the future.