Three new copper(ii) coordination compounds formulated as [Cu(H1.5bdea)2](hba)·2H2O (1), [Cu2(μ-Hbdea)2(aca)2]·4H2O (2), and [Cu2(μ-Hbdea)2(μ-bdca)]n (3) were generated by aqueous medium self-assembly synthesis from Cu(NO3)2, N-butyldiethanolamine (H2bdea) as a main N,O-chelating building block and different carboxylic acids [4-hydroxybenzoic (Hhba), 9-anthracenecarboxylic (Haca), or 4,4'-biphenyldicarboxylic (H2bdca) acid] as supporting carboxylate ligands. The structures of products range from discrete mono- (1) or dicopper(ii) (2) cores to a 1D coordination polymer (3), and widen a family of copper(ii) coordination compounds derived from H2bdea. The obtained compounds were applied as bioinspired homogeneous catalysts for the mild C-H functionalization of saturated hydrocarbons (cyclic and linear C5-C8 alkanes). Two model catalytic reactions were explored, namely the oxidation of hydrocarbons with H2O2 to a mixture of alcohols and ketones, and the carboxylation of alkanes with CO/S2O82- to carboxylic acids. Both processes proceed under mild conditions with a high efficiency and the effects of different parameters (e.g., reaction time and presence of acid promoter, amount of catalyst and solvent composition, substrate scope and selectivity features) were studied and discussed in detail. In particular, an interesting promoting effect of water was unveiled in the oxidation of cyclohexane that is especially remarkable in the reaction catalyzed by 3, thus allowing a potential use of diluted, in situ generated solutions of hydrogen peroxide. Moreover, the obtained values of product yields (up to 41% based on alkane substrate) are very high when dealing with the C-H functionalization of saturated hydrocarbons and the mild conditions of these catalytic reactions (50-60 °C, H2O/CH3CN medium). This study thus contributes to an important field of alkane functionalization and provides a notable example of new Cu-based catalytic systems that can be easily generated by self-assembly from simple and low-cost chemicals.