A new dipodal ligand, N,N'-bis{2-[(2-hydroxybenzylidine)amino]ethyl}malonamide (BHAEM) was synthesized by Schiff base condensation of N,N'-bis(2-aminoethyl)malonamide with two equivalent of salicylaldehyde and characterized on the basis of elemental analyses and various spectral (UV-vis, IR, (1)H NMR and (13)C NMR) data. The complexation reaction of the ligand with H(+), Co(II), Ni(II), Cu(II) and Zn(II) in solution was investigated by spectrophotometric and potentiometric method. Two protonation constants of BHAEM assigned for two hydroxyl groups of aromatic ring were determined and its hydrolysis mechanism was proposed through potentiometric result. In presence of metal ions, BHAEM shows different coordination properties. All metal ions form ML type complex where the ligand coordinates to the metal ion through two N-amine and two O-phenolate groups. In addition, Ni(II) and Cu(II) form additional complex species of the type MLH(-1) and MLH(-2), respectively due to ionization of amide protons. The molecular geometry of BHAEM was examined theoretically using the molecular mechanics MM3 force field followed by semi-empirical PM3 method and various spectral data UV-vis, IR and (1)H NMR were calculated from the energy-minimized structure applying semi-empirical ZINDO, PM3 and TNDO/2 method, respectively and compared with the experimental data. The probable structure of metal complexes in solution were proposed through calculated minimum strain energy by applying molecular mechanics MM(+) force field coupled with molecular dynamics simulation. Further the proposed structure of Cu(BHAEM) was refined through semi-empirical AM1/d method.