By the method of self-assembly of the reacting components in the systems “GeCl4 — pyridinoylhydrazones 2-hydroxybenz- (a-, p-, y-H2Ls) and 2-hydroxy- 1-naphth-aldehydes (H2Lnf) — CoCl2 - methanol” six complexes of the composition [Co(Cl)(H2O)(|i-Ls)2Ge]Cl 2H2O (I-III) and [Co(Cl)(H2O)(p-Lnf)2Ge]C12H2O (IV-VI) have been synthesized. Their electrolytic dissociation type and thermolysis character have been stated. It has been stated by the methods of IR spectroscopy, diffuse reflectance spectra, and magnetic susceptibility measurements two ligands in the (I-VI) to be bridged, doubly deprotonated (Ls2_, Lnf2 ), and tridentately linked to germanium (O(C-O) - N(ch=n) – O (Ph-O)) and monodentately linked to cobalt ion via pyridine nitrogen atom. At that germanium geometry holds the octahedral (Ge04N2) and cobalt one forms the tetrahedral shape.