The synthesis and characterization of four copper(II) complexes with different terpyridyl ligands have been carried out, their crystal and molecular structures determined and their magnetic and luminescent properties analyzed. The ligands used in the coordination reactions were 4′-(3-methyl-2-thienyl)-4,2′:6′,4″-terpyridine (4-stpy), -4′-(4-quinolinyl)-4,2′:6′,4″-terpyridine (4-qtpy), 4′-(4-quinolinyl)-3,2′:6′,3″-terpyridine (3-qtpy, unreported so far) and 4′-(4-cyanophenyl)-4,2′:6′,4″-terpyridine (4-cntpy); the reaction of these ligands with Cu(II)-hexafluoroacetylacetone (Cu(hfacac)₂) gives rise to coordination polymers Cu(4-stpy)(hfacac)₂ (I), Cu(4-qtpy)(hfacac)₂ (II), Cu(3-qtpy)(hfacac)₂ (III) and Cu(4-cntpy)(hfacac)₂ (IV). The different location of the nitrogen atom of the outer ring is responsible for the different coordination modes. The emission spectra of dichloromethane solutions are consistent with dissociation of the complexes; the emission maxima simulate those of the free ligands. The emission of I, III and IV in the solid state is essentially quenched upon complexation with Cu(II), whereas for compound II an emission at 420 nm is observed. The interaction between copper centers has been related with the coplanarity of terpyridine rings. Complexes I-III exhibit a paramagnetic behavior, while compound IV, with the smallest torsion angle between pyridine moieties, shows an antiferromagnetic behavior described by a dimeric model, with J=-4.38 cm^-1, g=2.06 and ρ=0.07.