We report the preparation of plant oil based triblock copolymers based on soybean oil monomers. The monomers were polymerized via atom transfer radical polymerization with subsequent chain extension, resulting in poly(styrene-b-soybean oil acrylate-b-styrene) (PS-b-PSBA-b-PS) and poly(styrene-b-soybean oil methacrylate-b-styrene) (PS-b-PSBMA-b-PS) triblock copolymers. These polymers, ranging from thermoplastics to thermoplastic elastomers (TPEs), were obtained by tuning molecular structures. We employed a “click coupling” strategy using triazolinedione (TAD) chemistry to create chemical junctions between the soft middle blocks of the triblock copolymers, which behave similar to physical chain entanglements. This method helps to overcome the drawbacks of plant oil based polymers, allowing for increase of tensile strength without sacrificing elongation. Cyclic tensile tests show that the “click coupled” triblock copolymers exhibit excellent elastic recovery characteristics.