Two new copper(II) complexes of composition [trans-Cu(en) 2(H 2O) 2](L 1) 2, 1 and [trans-Cu(en) 2(H 2O) 2](L 2) 2, 2 (L 1 = 3-methoxybenzoate, L 2 = 3,4,5-trimethoxybenzoate) were obtained by the addition of ethylenediamine to hydrated Cu(II) benzoates, Cu(L 1/L 2) 2·H 2O in methanol–water mixture. The newly synthesized complexes have been characterized by elemental analyses, spectroscopic techniques (electronic and FT-IR), magnetic moment determination and molar conductance studies. The complex 1 crystallizes in the triclinic system with space group P 1 ¯ and complex 2 crystallizes in the monoclinic system with space group P2 1/ c. X-ray structure determination revealed ionic structures consisting of one complex cation [Cu(en) 2(H 2O) 2] 2+ and two respective aryl benzoate anions in 1 and 2. There is a slight difference in the interplanar (plane passing through the Cu centers) distance between two cationic layers of both the complexes due to presence of two more OCH 3 groups on the anionic moiety in 2. A three dimensional hydrogen bonding network formed by N H⋯O and O H⋯O through second sphere and C H…π interactions besides electrostatic forces of attraction stabilizes crystal lattice in both the complexes.