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The paper provides a detailed overview of heterogeneous chemical reactions leading to the electrode surface modification and further reactivity of various functionalized surfaces. Notably, the present paper is different from other typical reviews and books about chemically modified electrodes—it is not aimed at highlighting the recent achievements in the research area, but provides a detailed analysis of the area background produced about 30–50 years ago. While there are many reviews on the present state-of-the-art (mostly describing specific applications), the background of the research area is not well remembered, particularly by young researchers and students. Therefore, the paper is mainly aimed at educational aspects, rather than highlighting the modern applications, which are only briefly mentioned in the concluding section. The chemical structures exemplified in the paper represent a comprehensive …