Reactions of lanthanide chlorides, copper hydroxycarbonate and 3,5-pyrazole dicarboxylic acid (H3pdc) under hydrothermal conditions result in six new 3d-4f heterometallic coordination polymers with two types of structures. Compounds [CuLn2(pdc)2(Hpdc)(H2O)4]·2H2O (Ln = Tb (), Dy (), Er (), and Y () exhibit a layered porous structure, made up of Cu(II)Ln(III) di-nuclear units which are connected by protonated Hpdc(2-) ligand, while the others [Cu3Ln4(pdc)6(H2O)8] (Ln = Eu (), Gd ()) display a three-dimensional (3-D) framework structure, in which six Cu(II)Ln(III) di-nuclear units are cross-linked by two coordinated lanthanide atoms. The catalytic properties of are investigated showing its activity and recyclability in the reaction of cyclopropanation of styrene.