Novel calix[4]pyrrole bearing vic-dioxime ligand (LH 2 ) of the general formula, R 1 R 2 C 2 N 2 O 2 H 2 (where, R 1 =C 6 H 5 - and R 2 =C 39 H 50 N 5 -) has been synthesized by the reaction of anti-chlorophenylglyoxime with 3-aminophenylcalix[4]pyrrole at room temperature. The mononuclear Cu(II), Ni(II) and Co(II)complexes of this vic-dioxime ligand were prepared and their structures were confirmed by elemental analysis, FT-IR, TGA and magnetic susceptibility measurements; the HMBC, DEPT, 1 H and 13 C NMR spectra of the LH 2 ligand were also reported. The electrochemical property of the complexes was investigated in DMSO by cyclic voltammetry at 200mVs −1 scan rate. The cyclic voltammetric measurements clearly indicated that Co(LH) 2 ·2H 2 O complex differs from the Ni(LH) 2 and Cu(LH) 2 complexes upon the exhibition of quasi-reversible one-electron transfer reduction process in the negative region instead of an irreversible process.