A new complex [Co(DH)₂(Thio)₂]₂[FeF ₅(H₂O)] • 2CH₃OH (where DH^- is dimethylglyoxime monoanion, Thio is thiourea molecule) was synthesized and its structure was determined. The coordination polyhedron of the Co(III) atoms in two centrosymmetric complex cations is an octahedron, formed by four N atoms of two dimethylglyoxime residues and two S atoms of coordinated Thio molecules. One of the Thio molecules is almost perpendicular to a metal cycle (the dihedral angle 87.8(1)°), which is responsible for realization of intermolecular hydrogen bond N-H•••O (N•••O 2.990(3) Å). The second Thio molecule is almost parallel to the equatorial CoN₄ fragment (the dihedral angle 159.4(1)°) to give rise to intramolecular π-π interaction between practically planar Thio molecule and one of the π-delocalized metal cycle. The Fe(III) coordination polyhedron is an octahedron, formed by five F atoms and by the O atom of coordinated water molecule. The key role in the crystal structure organization is played by intermolecular hydrogen bonds N-H•••F, N-H•••O, N-H•••S, the intramolecular bonds O-H•••O, formed by the donor NH₂ groups of a complex cation with the F atoms of the [FeF₅(H₂O)]^2- and the donor-acceptor groups of the Thio fragments.