Mechanistic studies of electrochemical proton coupled electron transfer (PCET) have attracted attention for many decades due to their importance in many fields ranging from electrocatalysis to biology. However, mechanistic research is confined to only a few groups, and challenges in this field can be found in both theory and experiment. The contributions to mechanistic studies of electrochemical PCET reaction in this thesis can be categorized under the following two headings: 1) mechanistic studies of an aminobenzoquinone modified monolayer system with multiple electron/proton transfer reaction; 2) studies that attempt to develop the relationship between thermochemical data and electrochemical PCET mechanism. An aminobenzoquinone modified monolayer showing nearly ideal electrochemical behavior and high stability was successfully prepared and used as a model system for the mechanistic study of electrochemical multiple electron/proton transfer. This model system has been proposed to undergo a 2e3H transfer at low pH electrolyte and a 2e2H transfer at high pH electrolyte. Two non-destructive electrochemical techniques (cyclic voltammetry and chronocoulmetry) have been applied for the measurement of apparent standard rate constant as a function of pH. Both pH dependent apparent formal potential and pH dependent apparent standard rate constant have been used to determine the charge transfer mechanism of this monolayer system. Under the assumption of an operative PCET mechanism (i.e. electron transfer step is the rate determining step), a theoretical description of this system has been developed based on the refinement and extension of previous models. By combining this extended theoretical model with pH dependent apparent formal potential and apparent standard rate constant, charge transfer pathways have been determined and shown to be consistent with the observed pH dependent electrochemical response, in addition, the determined pathways in this aminobenzoquinone modified monolayer are similar to previous reported pathways for benzoquinone freely dissolved in aqueous buffered electrolyte. A series of analytical expressions built in this thesis demonstrate that the parameters that differentiate stepwise mechanisms from concerted mechanisms can be classified into two aspects: thermodynamic parameters, namely acid dissociation constants, standard formal potentials; and kinetic parameters, namely standard rate constants, standard transfer coefficients. Although attempts to understand the relation between controlling parameters and electrochemical PCET mechanism (stepwise versus concerted) has been reported previously by some groups, there are still lots of unresolved aspects requiring further investigation. In this thesis, an important conclusion has been drawn which is that for the stepwise mechanism, an apparent experimentally observable kinetic isotope effect (KIE) can be induced by solvent isotope induced variation of acid dissociation constants, which contradicts previous understanding. Additionally, for the first time, values of apparent KIE, which were measured for the aminobenzoquinone modified monolayer system with stepwise PCET mechanism, were successfully explained by variation in acid dissociation constants, not by variation in standard rate constants. Based on theoretical prediction, a nitroxyl radical modified bilayer showing one electron one proton transfer reaction has been prepared in an effort to afford experimental verification. After applying similar analytical procedures as those for the aminobenzoquinone modified monolayer system, this bilayer system has been shown to follow the concerted 1e1H transfer pathway in high pH electrolytes. These latter contributions provide evidence that further development in this field will eventually lead to a comprehensive theory that can use known thermochemical variables to fully predict PCET mechanism.