The precise use of a widely available and inexpensive metallocene catalyst enabled the synthesis of isotactic polypropylene copolymers characterized by the copresence of randomly distributed cyclic units in the backbone and unsaturated pendant units employing 1,5-hexadiene as comonomer. Optimization of the polymerization conditions avoided the cross-linking phenomena that negatively affects the material processing and final properties, resulting in good yields of samples featuring high molecular masses and a precisely controlled microstructure. Such polypropylene-based copolymers exhibit a broad spectrum of properties ranging from thermoplastic to surprising elastomeric behavior, with the additional value of being functionalizable by post-polymerization reactions.