The coordination compounds [Co(DH)₂(An)₂][PF ₆] (I) and [Co(NioxH)₂(Thio)₂][PF₆] · 0.5DMF · 0.5H₂O (II), where DH- and NioxH-are dimethylglyoxime and 1,2-cyclohexanedione dioxime monoanions, respectively; An is aniline; and Thio is thiourea, were synthesized. The composition and structure of the complexes were determined by elemental analysis, IR spectroscopy, and X-ray diffraction. Compounds I and II are ionic and consist of complex cations [Co(DioxH)₂(A)₂]⁺, where DioxH is the α-dioxime residue, A is neutral organic molecule (aniline or thiourea), and [PF₆]^- anions. The coordination polyhedra of the Co(III) complex cations are octahedra formed by the set of N6 donor atoms of monodeprotonated DH-residues and two An molecules (in I) or by the N ₄S₂ atoms of two NioxH-anions and two Thio molecules (in II). The formation of the crystal structure of I and II is largely determined by the [PF₆]-anions in which the fluorine atoms serve as acceptors in various hydrogen bonds. The compounds were tested as stimulators of biosynthesis of extracellular proteases of the micromycete Fusarium gibbosum CNMN FD 12. The introduction of the test complexes in optimized concentrations into the nutrition medium for cultivation of the producing strain enhances the biosynthesis of acid and neutral proteases by 63.6 and 92.5%, respectively.