Pd complexes with diimine ligands promote controlled cyclopolymerization of 1,6-dienes and 1,6,11-trienes to afford the polymers containing 1,2-trans-cyclopentane groups with well-regulated stereochemistry. Copolymerization of the dienes with ethylene and α-olefins also proceeds to give functionalized polyolefins. The polymerization of the monomers with oligomethylene spacer yields the polymers with five-membered rings in accurate density and distribution along the polymer chain. 4-Alkylcyclopentenes and alkenylcyclohexanes also get polymerized by the Pd complex to afford polymers with 1,3-trans-cyclopentane groups and 1,4-trans-cyclohexane groups, respectively. Isotactic polymer of 4-alkylcyclopentenes show liquid crystalline properties.