The influence of the supporting electrolyte and the solvent of crystallisation on the nature of cadmium complexes of 2,6-bis(1-salicyloylhydrazonoethyl)pyridine (H4daps), obtained by an electrochemical procedure, has been investigated. [Cd(H2daps)(H2O)2] (1), [Cd(H2daps)(H2O){(CH3)2CHOH}] (2), [Cd(H3daps)Cl]·CH3CN·0.25H2O (3), [Cd(H3daps)Cl(CH3OH)]·2H2O·CH3OH (4), and [Cd(H2daps)Cl(H2O)]N(CH3)4 (5), have all been isolated and crystallographically characterised. X-ray diffraction studies show that the cadmium atom in 3 is in an unusual pentagonal pyramidal [CdN3O2Cl] geometry, while in the other compounds the cadmium atom is in a bipyramidal pentagonal environment. The organic ligand acts as a pentadentate dianionic ligand in 1, 2, and 5, and as a pentadentate monoanionic ligand in 3 and 4.