This article provides an overview of polybutadiene materials as a progression from the monomer 1,3‐butadiene to a useful polymer product with a wide range of applications. A brief history of polybutadiene, with its development as a high cis ‐polybutadiene material during World War I through its present day use as a high vinyl substitute for styrene–butadiene rubber is included. The structure and properties of the monomer are presented, along with monomer manufacture, typical specifications, and health and safety issues. Following a detailed discussion on both polymer microstructure and macrostructure, there is an in‐depth review of polymerization methods that are typically used to produce polybutadiene. The state‐of‐the‐art in free‐radical, Ziegler–Natta, anionic, and cationic polymerization techniques that produce polybutadiene are thoroughly discussed in terms of the influence of catalyst/initiator technology on microstructure and the resulting relationship between microstructure and applications. The most popular commercial polymerization processes are also reviewed including solution, emulsion, and an introduction to gas‐phase polybutadiene polymerization technology. Finally, the economic aspects of polybutadiene materials are presented, including major producers, capacities, and pricing.