Abstract New copper(II) catalytic systems for the mild oxidative C–H functionalization of cycloalkanes and cycloalkenes were developed, which are based on a series of mixed-ligand aminoalcohol-dicarboxylate coordination polymers, namely [Cu₂(μ-dmea)₂(μ-nda)(H₂O)₂]_n·2nH₂O (1), [Cu₂(μ-Hmdea)₂(μ-nda)]_n·2nH₂O (2), and [Cu₂(μ-Hbdea)₂(μ-nda)]_n·2nH₂O (3) that bear slightly different dicopper(II) aminoalcoholate cores, as well as on a structurally distinct dicopper(II) [Cu₂(H₄etda)₂(μ-nda)]·nda·4H₂O (4) derivative [abbreviations: H₂nda, 2,6-naphthalenedicarboxylic acid; Hdmea, N,N′-dimethylethanolamine; H₂mdea, N-methyldiethanolamine; H₂bdea, N-butyldiethanolamine; H₄etda, N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine]. Compounds 1–4 act as homogeneous catalysts in the three types of model catalytic reactions that proceed in aqueous acetonitrile medium under mild conditions (50–60°C): (i) the oxidation of cyclohexane by hydrogen peroxide to cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone, (ii) the oxidation of cycloalkenes (cyclohexene, cyclooctene) by hydrogen peroxide to a mixture of different oxidation products, and (iii) the single-pot hydrocarboxylation of cycloalkanes (cyclopentane, cyclohexane, cycloheptane, cyclooctane) by carbon monoxide, water, and a peroxodisulfate oxidant into the corresponding cycloalkanecarboxylic acids. The catalyst and substrate scope as well as some mechanistic features were investigated; the highest catalytic activity of 1–4 was observed in the hydrocarboxylation of cycloalkanes, allowing to achieve up to 50% total product yields (based on substrate).