Solid-state stereochemistry and mobility of paramagnetic copper(II) complexes formed by aliphatic amino acids (L-alanine, D,L-alanine, 1-amino-2-methyl-alanine) and 1-amino(cyclo)alkane-1-carboxylic acids (alkane = propane, butane, pentane, hexane) as bidentate ligands has been studied by C-13 and H-2 solid-state fast magic angle spinning (MAS) NMR spectroscopy. We examined the prospective method to characterize solid-state paramagnetic compounds in a routine way. Both C-13 and 2H MAS spectra can distinguish D,L, and L,L, diastereomers of natural and polydeuterated bis([D-n]alaninato)copper(II) (n = 0, 2, 8) complexes with axial and/or equatorial methyl positions (conformations) primarily due to different Fermi-contact (FC) contributions. The three-bond hyperfine couplings clearly show Karplus-like dependence on the torsional angles which turned out to be a useful assignment aid. Density functional theory calculations of the PC term and crystal structures were also used to aid the final assignments. The correlations obtained for bis(alaninato-kappa N-2,O)copper(II) complexes were successfully used to characterize other complexes. The usefulness of the 2H MAS spectra of the deuterated complexes was underlined. Even the spectra of the easily exchangeable amine protons contained essential stereochemical information. In the case of a dimer structure of bis(1-aminohexane-1-carboxylato-kappa N-2,O)copper(II) both the 13C and 2H resolutions were good enough to confirm the presence of the cis and trans forms in the asymmetric unit. With regard to the internal solid-state motions in the crystal lattice, the obtained quadrupolar tensor parameters were similar for the D,L- and L,L-alaninato isomers and also for the cis trans forms suggesting similar crystal packing effects, static amine deuterons involved in hydrogen bonding, and fast rotating methyl groups.