Research activities at laboratory of polymer materials chemistry, Nagaoka University of Technology is briefly introduced. The key concept of our laboratory is “Creation of new polymer that never exists” and the motivation for the research activities is based on the curiosity to explore the possibility of polymerization of new conjugated dienyl monomers containing functional groups. Through the study of dienyl monomers containing functional groups, we have found that introduction of functional groups sometimes dramatically changes the stability and polymerizability of monomers. Although 2-ethoxycarbonyl-1,3-butadiene is not stable at room temperature, its equivalent, 2-triethoxymethyl-1,3-butadiene, is stable and can be polymerized by free-radical initiator to give polydienes containing ester function in every repeating unit. Alkoxysilyl groups attached to the 2-position of 1,3-butadienyl framework decreased the reactivity of active chain-end carbanion in the anionic polymerization. The microstructure was controlled to cis-1,4 if the steric hindrance of alkoxy group is very large. 1,3-Butadiene derivative containing N,N-dialkyl amide group at 2-position can be polymerized by free-radical and anionic initiators but the microstructure of the resulting polymer changed depend on the condition. Current research topic such as polymerization of [3]dendralene derivatives are also described.