A series of styrene-butadiene di-block copolymers with high cis -1,4 unit content (greater than 92%) polybutadiene (PB) and isotactic-rich polystyrene (PS) ( mmmm > 65%) was synthesized using α-diimine nickel catalysts (Ni-diimine). Four different Ni-diimine catalysts were synthesized via a complexing reaction between nickel (II) naphthenate and laboratory-made α-diimine ligands L1, L2, L3 and L4, which have different steric volume structures. The results indicate that the Ni-diimine catalyst prepared using the L4 ligand with a higher steric volume can effectively initiate the block polymerization of butadiene and styrene, and the resulting polymer has distinguished cis -1,4 structure unit PB and high isotactic-selective PS block. Differential scanning calorimetry and electrochemical performance tests show that these block copolymers with cis -1,4-regulated and isotactic-selective polymerization have advantages in terms of high-temperature and low-temperature resistance as well as corrosion resistance. Therefore, these copolymers are expected to be widely used in some harsh industrial environments.