The proposed complex approach for studying electrode reactions and near-electrode phenomena combines the collective X, electrode and volume ECS, VCS, as well as characteristics x of molecular reactivity. This allows a more in-depth study of the mechanism of electrochemical transformations and the behavior of the medium at the boundary with the charged surface. The general strategy of the method can be written in a sequence (see text for details): a) conducting electrolysis under conventional "heterogeneous" conditions b) conducting the same process with homogeneous electron carrier HOMEC c) comparing the products of the two processes, x dir , x hom , general conclusion about the presence of electrode effects; if detected -conducting NELTO electrolysis with increasing HOMEC contribution d) in the case of changing the ratio of products, theoretical estimation of the length and profile of the reaction zone x = f(L), preliminary -to find the necessary kinetic characteristics e) comparison of x = f(L) with X = F(L), concluding on the nature of the near-electrode phenomena. The review provides an example on one type of reaction for a range of substrates, all steps a) -e) are performed.