Interactions of nano cobalt chloride in the absence and presence of Schiff base ligands derived from 4,6-diacetyl resorcinol are studied thermodynamically in mixed binary solvent (DMF-H₂O). The organic ligands are nominated as EAH₂DAR and O-PhenH₂DAR. The nano cobalt chloride was characterized by the TEM tool. The calculated parameters depend on the conductivity of solutions measured at different temperatures and concentrations. The study was done at 298.15, 308.15, 318.15, and 328.15 K in various concentrations of a mixed solvent of dimethylformamide and water. The association parameters such as the enthalpies, entropies, free energies of association, degree of association, and association constant were calculated in the absence and presence of Schiff base ligands. The results showed the strong electrolyte behavior of nano cobalt chloride in the absence and presence of organic ligands. The interactions between cobalt species increase after adding Schiff bases ligands where the degree of dissociation decreases in the presence of ligands. Small values of degree of dissociation and s of molar conductance show that the interactions increase in the case of O-PhenH₂DAR than EAH₂DAR ligand. The solution of nano cobalt chloride salt with O-PhenH₂DAR has the highest values of association constants and more negative Gibbs free energies at all temperatures and concentrations used.