By the way of reagents interaction the complexes of general formulas [Ge(-, - Ls·H)2][MCl4]·СН3ОН, where М = Со:  – (I),  – (II), М = Zn:  – (III); [Ge(-, - Lnf·H)2][MCl4], where М = Со:  - (IV),  - (V); М = Zn:  – (VI) were obtained from the systems «GeCl4 – 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde nycotinoyl-, isonycotinoylhydrazones (-, - H2Ls and -, - H2Lnf, respectively) – МCl2 (М = Со (II), Zn (II)) – СН3ОН». The electrolytic dissociation type and thermolysis mechanism were determined. By the methods of IR spectroscopy (I-VI), PMR (for Ge-Zn complexes III, VI) and X-ray absorption spectroscopy EXAFS (for Ge-Co complexes I, II, IV, V) it was determined that complexes I-VI have octahedral polyhedron {GeO4N2} due to O(C-O)-N(CH=N)-O(Ph-O) coordination of two hydrazone molecules which have two protonated exochelate nitrogen atoms Npy. In the IR spectra of I-VI are absent (OH), (NH), (C = O) and  (NH) compared to hydrazones, are present vibrations frequency the fragment C = NN = C (1600-1607 cm-1) and -N=CO- (1547-1545 cm-1), ν(Ge-O) ~ 680 cm-1 and ν(Ge←N) ~ 615 cm-1. Frequencies δ(Npy) rings increased by ~15 cm-1 compared to hydrazones (610, 900 cm-1), which confirms their protonation in the complexes. In PMR spectrums of Ge-Zn complexes (III, VI) the signals of NH-, Ar-OH groups protons are absent, НС=N shifted to 9,622 - 9,365 ppm and НN+py observes at 5.05 – 5.5 ppm. The formed germanium complex cation neutralize the charge [MCl4]2- . Given the coordination number of zinc and 3d10 configuration of zinc (II), [ZnCl4]2- has a tetrahedron structure. The electronic transitions (4А2g4T1g(F) and 4А2g4T1g(P)) observed in the diffuse reflection spectrums and эфф (4.01-4.38 BM, Т = 295К) values for Ge-Co complexes (I, II, IV, V) specify on the tetrahedron structure of the cobalt polyhedron. The local arrangements, bonds lengths and the germanium (IV) and cobalt (II) polyhedrons geometry were determined by EXAFS spectroscopy. MFT EXAFS GeK-edge for I-VI consist of base peak with r = 1.45 - 1.48 Å, corresponding scattering of photoelectronic wave on the six nearest atoms of nitrogen and oxygen ligands that make up the first coordination sphere, and peaks with smaller amplitude at large r. MFT EXAFS CoK-edge consist only of base peak with r = 1.79 - 1.83 Å approximately equal amplitude, which is well satisfies model of local atomic environment of the cobalt ion with four chlorine atoms. Bond lengths Со–Сl 2.25 - 2.26 Å.