Polymerization of 1,6-heptadiyne using an insoluble Zeigler-Natta catalyst affords soluble polymer having six-membered ring containing polyene. Ruthenium(II)-catalyzed reaction of a substituted 1,6-heptadiyne with norbornene affords a tandem [2+ 2+ 2]/[4+2] cycloaddition product and a [2+ 2+2] cycloadduct. Cyclocopolymerization of 1,6-heptadiyne with dipropargyl ether under nitrogen atmosphere using KSCN, KBr and KI as initiators in N,N-dimethyl formamide has been studied.