Isoprene polymerization was conducted in the cis‐1,4‐selective manner by combining neodymium chloride with 8‐hydroxyquinoline derivatives and activating the system with triisobutylaluminium. The neodymium‐based complex pre‐catalysts with 8‐hydroxyquinoline derivatives were synthesized and characterized as well as the molecular structure of a representative complex using single‐crystal X‐ray diffraction. All complexes exhibited high activity and stereospecificity (up to 97.3%) towards isoprene polymers with high molecular weight (105 g mol−1). The Al/Nd and isoprene/Nd molar ratios, reaction temperature and influence of 8‐hydroxyquinoline substituents were investigated for correlations with catalytic activities and molecular weights of the polyisoprenes obtained. © 2015 Society of Chemical Industry