ABSTRACT. Some five-coordinated cobalt(III) complexes were synthesized and characterized using elemental analysis, 1 H NMR and IR spectra. The formation constants and the thermodynamic parameters were measured spectrophotometrically for the 1:1 adduct formation of [Co(Chel)(PBu3)]ClO4.H2O where Chel = cd3OMesalen, cd4OMesalen, cd5OMesalen: methyl-2-{[1-methyl-2-(2-hydroxy-3-, 4-, 5-methoxyphenyl)methylidynenitrilo]ethyl}amino-1-cyclopentene-dithiocarboxylate, as acceptors, with some linear and cyclic amines as donors, in different solvents at constant ionic strength (I = 0.1 M NaClO4), and at various temperatures (T = 283-313 K). The results revealed that the formation constants of the Co(III) Schiff base complexes toward a given amines donor are as follow:The trend of the formation constants of the donors (amines) toward a given cobalt(III) complex is as follow: Im > 4-MeIm > BzIm and n-butylamine > sec-butylamine > tert-butylamine. Also the effect of the solvents on the formation constants of a given cobalt(III) Schiff base complex toward a given donor are as follow: CH3CN > DMF > EtOH. The ligands and their cobalt complexes have been screened for their antibacterial activities. All the free Schiff base ligands exhibit higher antibacterial activity than the cobalt(III) complexes.