The recent achievements of electrochemical functionalization of C—H bonds in aromatic substrates containing the pyridine moiety and acting as a ligand directing substitution to the ortho-position in the presence of the palladium and nickel compounds are analyzed and generalized in the review. Acetoxylation, perfluoroacetoxylation, perfluoroalkylation, and phosphorylation are considered for 2-phenylpyridine (PhPy) as an example. The PdII metallocycles with the Pd-bound acetate, perfluoroacetate, and perfluoroheptanoate substituents were isolated and characterized as possible intermediates: binuclear [(PhPy)Pd(µ-OAc)]2 and [(PhPy)Pd(µ-TFA)]2 and mononuclear [(PhPy)Pd(TFA)](MeCN), [(PhPy)Pd(TFA)](PhPy), [(PhPy)Pd(PFH)](PhPy), and [(PhPy)Pd(EtO)2P(O)]2. Their electrochemical properties were studied. The fluorinated derivatives are in solvent-dependent equilibrium between the mononuclear and binuclear forms. Cyclic voltammetry was used to establish the redox properties of the palladium cycles and routes of their oxidation to the final products. A new approach to CH-substitution products based on the electrochemical generation of Pd or Ni in high oxidation states in the presence of substrate-ligand was proposed.