Two new copper(II) complexes comprising of coordinated and non-coordinated p-toluenesulfonate, [trans-Cu(γ-pic) 2 (H 2 O) 4 ](pts) 2 ·2H 2 O, 1 and [trans-Cu(γ-pic) 4 (pts) 2 ]·2H 2 O, 2 (where p-toluenesulfonate=pts and γ-picoline=γ-pic) have been isolated from the same reaction mixture. These complexes have been characterized by spectroscopic techniques, molar conductance, TGA, magnetic susceptibility studies, and single crystal X-ray structure determination. Both complexes crystallize in the monoclinic crystal system with P2 1 /c space group having cell dimensions of a=8.0203(2)Å, b=19.4471(4)Å, c=10.3000(3)Å, β=93.4420(9)°, V=1603.61(7)Å 3 , (Z=2) in 1 and a=10.1473(2)Å, b=10.9948(2)Å, c=18.0952(5)Å, β=93.0340(9)°, V=2015.96(8)Å 3 , (Z=2) in 2. Single -crystal X-ray structure determinations revealed the presence of ionic complex, viz: one complex cation [trans-Cu(γ-pic) 2 (H 2 O) 4 ], two pts anions and two water molecules of crystallization in the complex 1 and neutral [trans-Cu(γ-pic) 4 (pts) 2 ] and two water molecules of crystallization in 2. The crystal packing in both complexes is stabilized by OH⋯O, CH⋯O hydrogen bonds and CH⋯π interactions.