Mechanical and viscoelastic properties of polybutadiene-based rubber materials are highly dependent on polybutadiene microstructure along with molar mass, dispersity, polymer architecture and styrene content for copolymers. In addition, the living character of anionic polymerization of butadiene allows the precise chain-end functionalization and synthesis of block copolymers. Knowing that mainly the nature of the counter-ion or solvents influence strongly the polybutadiene microstructure, a summary of all anionic or related strategies is proposed in this review to tune polybutadiene microstructures. The influence of alkali metals, alkaline earth metals and multi-metallic compounds as well as their environment is discussed. (C) 2018 Elsevier Ltd. All rights reserved.