New methylene bridged bis(tridentate) binucleating ligands, bis[2-hydroxy-5-chloro{(4-methyl-piperazin-1-yl)methyl} phenyl]methane (L 1 H 2 ), bis[2-hydroxy-3-{(1-imino-N,N-dimethyl aminopropyl)ethyl}-5-chlorophenyl]methane (L 2 H 2 ) and bis[2-hydroxy-3-{(1-imino-N,N-diethylaminopropyl)ethyl}-5-chlorophenyl] methane (L 3 H 2 ) and their copper(II) complexes have been synthesised and reported. These complexes have been characterised by elemental analysis, electronic and ESR spectroscopy. The binuclearity of these complexes were confirmed by FAB mass spectroscopy. Electrochemical studies of the complexes suggested that the reduction processes are quasi-reversible single step two electron transfer Cu I I Cu I I /Cu I Cu I at negative potentials (-0.2 to -0.6 V). The magnetic moment μ e f f (per Cu) for these complexes at 298 K are found in the range 1.71 to 1.83 B.M. Variable temperature magnetic susceptibility measurements revealed the absence of exchange coupling between Cu I I centres. ESR spectra of these complexes at liquid nitrogen temperature (77 K) are similar to mononuclear copper(II) complex with nuclear spin 32.