We have described the effect of electric fields on the electrostatic surface potential at the MIEC-gas interface. By integrating an electric field with first principles calculations, we validated the model to correctly predict the nature of the electrostatic surface potential for three experimentally studied systems. Furthermore, we have determined a link between the electrostatic surface potential and the mechanistic nature of the rate limiting charge transfer reaction, where we illustrated the importance of decoupled charge transfer for optimum kinetics. These kinetic effects may also be applied to other MIEC systems for energy storage and conversion.