1,3-Butadiene is polymerized in a hydrocarbon solvent using a catalyst
system containing (A) a cobalt salt, (B1) a phosphine compound having one branched
aliphatic group of 3 or more carbon atoms or one alicyclic group of 5 or more carbon
atoms and two aromatic groups, and (C) an organic aluminum compound, or a catalyst
system containing (A) a cobalt salt, (B) (B1) a phosphine compound having one branched
aliphatic group of 3 or more carbon atoms or one alicyclic group of 5 or more carbon
atoms and two aromatic groups and/or (B2) a triarylphosphine compound having three
aromatic groups, (C) an organic aluminum compound and (D) an active halogen-containing
compound, thereby obtaining crystalline 1,2-polybutadiene.