In recent years, electrolytic plasma polishing technology has attracted wide attention due to its advantages of shape adaptability, high efficiency, better precision, environmental friendliness, and non-contact polishing. However, the lack of research on the evolution mechanism of the gas layer at the anode interface restricts the improvement of the material removal mechanism and the regulation of the polishing effect. Firstly, the thermodynamic conditions of gas layer formation were analyzed based on the Clapeyron-Clausius equation, and the key parameters affecting the gas layer were identified. Secondly, the laws of voltage and electrolyte temperature on the dynamic evolution of the gas layer and its polishing effect were revealed. Additionally, the influence of the gas layer on the voltage-current characteristics was also investigated by analyzing the experimental phenomena. The results indicate that the optimal polishing effect is achieved at a voltage level of 300 V resulting in a decrease in Ra from 0.451 μm to 0.076 μm. Similarly, superior polishing results are obtained when the electrolyte temperature is 80 °C, with a decrease in Ra from 0.451 μm to 0.075 μm. This study provides theoretical guidance for the further development and application of electrolytic plasma polishing technology.