The aza-14-crown-4 with the di(α-pyridyl)-substituted bispidine subunit (L) and its cationanion complex with cobalt(II) chloride of composition [Co(L)(H2O)][CoCl4] (I) have been synthesized. The structure of compound L has been proved by IR spectroscopy, NMR, and mass spectrometry. X-ray crystallography has demonstrated that the L molecule in the complex is an NNNN-tetradentate chelating ligand, and the crown ether moiety is not directly bound to the metal cation. In the cationic moiety of the complex, the Co(1) atom has an octahedral environment, and the Co(2) polyhedron in the anionic moiety is a tetrahedron. The cationic and anionic moieties of complex I are linked by the bridging chlorine atom. © 2013 Pleiades Publishing, Ltd.