The electron-transfer kinetics for each of three copper(II/I) tripodal ligand complexes reacting with multiple reducing and oxidizing counter reagents have been examined in aqueous solution at 25 degreesC, mu = 0.10 M. For all of the ligands studied, an amine nitrogen serves as the bridgehead atom. Two of the ligands (PMMEA and PEMEA) contain two thioether sulfurs; and one pyridyl nitrogen as donor atoms on the appended legs while the third ligand (BPEMEA) has two pyridyl nitrogens and one thioether sulfur. Very limited kinetic studies were also conducted on two additional closely related tripodal ligand complexes. The results are compared to our previous kinetic study on a Cu(II/I) system involving a tripodal ligand (TMMEA) with thioether sulfur donor atoms on all three legs. In all systems, the Cu(II/I) electron self-exchange rate constants (k(11)) are surprisingly small, ranging approximately 0.03-50 M-1 s(-1). The results are consistent with earlier studies reported by Yandell involving the reduction of Cu(II) complexes with four similar tripodal ligand systems, and it is concluded that the dominant reaction pathway involves a metastable (CuL)-L-II intermediate species (designated as pathway B), Since crystal structures suggest that the ligand reorganization accompanying electron transfer is relatively small compared to our earlier studies on macrocyclic ligand complexes of Cu(II/I), it is unclear why the k(11) values for the tripodal ligand systems are of such small magnitude.