The Schiff base (HL) formed by condensation of ferrocenylamine with salicylaldehyde has been used for the preparation of complexes with CoII, NiII, CuII, and ZnII of formula [ML2]. The ligand HL is stable in the solid state and easily hydrolyzed in solution with formation of the free N-base. This hydrolysis has been studied kinetically in a water–acetone acidic medium. A single-crystal X-ray study of HL [orthorhombic, space group Pca21, a= 16.229(2), b= 5.914(1), c= 14.516(2)A, α=β=γ= 90°, and Z= 4] indicates almost coplanarity between the chelating N–C–C–O moiety and the adjacent cyclopentadienyl ring of ferrocene, with the H atom of the hydroxyl group bridging between the N and O atoms. An X-ray study has been also carried out on the complex [CuL2[monoclinic, space group P21/c, a= 12.668(2), b= 10.422(2), c= 20.921 (3)A;, α=γ= 90, β= 91.10(1)°, and Z= 4] in which CuII has a distorted tetrahedral environment. On the basis of the available information, i.e. X-Ray, visible spectral, and magnetic susceptibility data, all the [ML2 complexes can be assigned a tetrahedral or pseudo-tetrahedral structure. Cyclic voltammetric experiments in dimethylformamide have been performed mainly to examine the FeII→ FeIII one-electron oxidation in HL and its [ML2] complexes, and the results are compared to those previously obtained for ferrocenylamine and other monosubstituted ferrocene derivatives.