Abstract The thermodynamics of the electrode/electrolyte interface have been described for a two‐electrode cell, using a classical Guhemian approach. The description has been related to a two‐electrode cell that frequently is employed for enzyme electrodes. Theoretical considerations of the electrical double layer have been correlated with conditioning pretreatment regimes for the preparation of enzyme electrode cells. Effects of electrolyte composition and effects of concentration have been described. Consequently, improved methodologies have evolved for the pretreatment of pseudo reference/secondary electrodes, allowing the equilibration and subsequent use of sensors within <5 minutes as compared with previous requirements for full equilibration from open circuit.