Electrophoretic deposition (EPD) coating has become a hot topic due to its simple experiment, wide application, and wide material range. In this study, the PTFE coating was successfully prepared by electrophoretic deposition through the systematic study of electrophoretic deposition kinetics. In particular, in the dispersion system with ethanol as solvent, Nafion and NaOH were simultaneously added as additives to obtain a beneficial synergistic effect on PTFE electrophoretic deposition. And the best additive scheme is: when the concentration of PTFE was 6 g·L− 1 and the deposition time was increased to 20 min, adding 0.10 g·L− 1 Nafion and 0.10 mM NaOH simultaneously. Compared with the scheme with Nafion being only additive, the addition of NaOH can improve the deposition rate from 0.16 mg·cm− 2 to 0.98 mg·cm− 2, and the deposition rate increases by about 6 times. According to electrophoretic deposition kinetics, there is an obvious critical transition time between linear and parabolic regions in the preparation of the coating. Prolonging the arrival of critical transition time is beneficial to effectively achieve stable growth of the coating in a longer time. It is found that a more ideal additive can not only increase the deposition rate of coating, but also significantly accelerate the arrival of critical transition time. Meanwhile, the deposition voltage also has an important influence on the critical transition time. Increasing the voltage can improve the deposition speed but shorten the critical transition time. Therefore, the application of deposition voltage needs to strike a balance between deposition rate and critical time point. The optimal deposition conditions proposed in this work are: deposition voltage 60 V, deposition time 20 min, additive 0.10 g·L− 1 Nafion and 0.10 mM NaOH.