The structural organization of the clathrates of bis(diethyldithiocarbamato)pyridinezinc(II) and -copper(II) with 1,2-dichloroethane, M(Edtc)2Py · L, was studied by EPR, high-resolution solid-state 13C and 15N NMR, and X-ray crystallography. The clathrates contain typical molecular channels and cavities, which accommodate chemically unbound dichloroethane molecules. At the molecular level, the geometry of the zinc and copper coordination polyhedra is intermediate between a trigonal bipyramid and a square pyramid. The ground state of the unpaired electron of copper(II) is a result of mixing the dx2-y2 and dz2 orbitals. The Edtc ligands incorporated in the zinc(II) clathrate are somewhat nonequivalent, both magnetically and structurally. The chlorine atoms of the 1,2-dichloroethane molecule are disordered over two structural positions with different occupancies, which may point to the occurrence of several conformations. The 13C and 15N NMR signals were assigned based on combined analysis of available structural and NMR data