Electrophoretic deposition (EPD) is the potential process in high porosity thin films’ fabrication or complex surface coating for perovskite photovoltaics. Here, the electrostatic simulation is introduced to optimize the EPD cell design for the cathodic EPD process based on functionalized multiwalled carbon nanotubes (f-MWCNTs). The similarity between the thin film structure and the electric field simulation is evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM) results. The thin-film surface at the edge has a higher roughness (Ra) compared to the center position (16.48 > 10.26 nm). The f-MWCNTs at the edge position tend to be twisted and bent due to the torque of the electric field. The Raman results show that f-MWCNTs with low defect density are more easily to be positively charged and deposited on the ITO surface. The distribution of oxygen and aluminum atoms in the thin film reveals that the aluminum atoms tend to have adsorption/electrostatic attraction to the interlayer defect positions of f-MWCNTs without individually depositing onto the cathode. Finally, this study can reduce the cost and time for the scale-up process by optimizing the input parameters for the complete cathodic electrophoretic deposition process through electric field inspection.