The acid-base equilibria of tetracycline and its copper(II) complex formation equilibria are investigated in dioxane-water mixtures. The ternary complexes of copper(II) with tetracycline as primary ligand and amino acid or DNA constituent as secondary ligand are studied in 50% dioxane-water solution. The formation constants of the ternary and binary complexes with amino acids or DNA constituents are determined. The concentration distribution of the various complex species are evaluated. Probable mode of chelation with tetracycline and DNA constituents is discussed.