Two new complexes [Cd(tmf)2(SCN)2]n(1) and [Ni(tmf)4(SCN)2](2) have been synthesized by self-assembly of ligand 1-[(1H-1,2,4-triazol-1-yl)methyl]ferrocene (tmf), SCN- anions and Cd(II) or Ni(II) cations. X-ray crystal diffraction reveals that complex 1 displays one-dimensional double chain structure; complex 2 is a two-dimensional supramolecule formed by hydrogen bonds. The results of the third-order NLO experiments display that the n2 values of complex 1 (2.11 × 10-11 esu) and 2 (1.92 × 10-11 esu) are close to the n2 value of tmf (2.49 ×10-11 esu). This indicates that the third-order NLO properties of complexes 1 and 2 are ruled by tmf ligand. The cyclic voltammetry (CV) studies suggest that the redox processes of complexes 1 and 2 at the electrode are controlled by diffusion. The results of chronoamperometry(CA) and chronocoulometry(CC) show that the values of the diffusion coefficient (D) of complex 1 is smaller than that of complex 2.