Benzoxazine-functionalized poly(styrene-b-butadiene-b-styrene) (SBS) has been successfully synthesized via the thiol-ene click reaction. Unlike the typical method for fabrication of blends of SBS and thermosetting resins, the benzoxazine could be directly attached on to the chains of PB domains of this triblock copolymer without any prechemical modification for SBS via the incorporation of thiol functionalized benzoxazine (PTMP-BZ). AFM characterization shows that both thiol-ene and subsequent benzoxazine ring-opening reactions have a profound influence on the final morphologies of SBS, which undergoes great change from the cylinders for the pure SBS to different types of lamella structure for the SBS with different contents of the benzoxazines and the results obtained from AFM indicate that the interaction between PB and PS domains is strengthened after two reaction steps and this is responsible for the substantial improvement on the mechanical properties of material including tensile strength and storage modulus. In the meantime, the resilence of SBS is also improved significantly by the incorporation of benzoxazine and the modified SBS blends could recover its original shape without residual elongation after the tests of cyclic tensile stress-strain.