Several new Cu(II) derivatives of the 1,3-bis(dimethylamino)-2-propanolato (bdmap) ligand with formula [Cu(2)(bdmap)(acac)(NH(3))(3)(MeOH)](ClO(4))(2), [Cu(2)(bdmap)(NO(2))(3)(H(2)O)](4) and [Cu(2)(bdmap)(OH)(ox)(0.5)(H(2)O)(2)](n)(ClO(4))(n)xnH(2)O were synthesized and characterized both structurally and magnetically. Dinuclear compound crystallizes in the monoclinic system, space group P2(1)/c, octanuclear compound crystallizes in the triclinic space group P1 and the 1-D alternating system crystallizes in the monoclinic system, space group P2/n. Magnetic analysis indicates strong antiferromagnetic coupling for all derivatives, mainly due to the interaction through the alkoxo O-atom of the bdmap ligand. The effect on the magnetic behaviour of the additional bridging ligands is analysed.