In this theoretical work, we present for the first time voltammetric results of a surface multistep electron transfer mechanism that is associated with a preceding chemical reaction that is linked to the first electron transfer step. The mathematical model of this so-called “surface CEE mechanism” is solved under conditions of square-wave voltammetry. We present relevant set of results portraying the influence of kinetics and thermodynamics of chemical step to the features of simulated voltammograms. In respect to the potential difference at which both electrode processes occur, we consider two different situations. In the first scenario, both peaks are separated for at least |150 mV|, while in the second case both peaks occur at same potential. Under conditions when both peaks are separated for at least |150 mV|, the first process can be described with the voltammetric features of a surface CE mechanism, while the second peak gets attributes of a simple surface electrode reaction. When both peaks take place at same potential, we elaborate an elegant methodology to achieve separation of both overlapped peaks. This can be done by modifying the concentration of the substrate “Y” in electrochemical cell that is involved in the preceding chemical reaction. The results of this work can be of big assistance to experimentalists working in the field of voltammetry of metal complexes and drug-drug interactions.