Thermoplastic elastomers (TPE) are an important class of polymers which are processed like thermoplastics, but behave as elastomers. Apart from their interesting properties they have great advantage of recycling and reuse during processing. Conventional diene based TPEs (like SBS triblock copolymers) have poor resistance to weatherability, thermo-oxidative degradation and importantly poor resistance to oils and fuels. The inception of very versatile controlled radical polymerization (CRP) processes in late 1990s has led to a great opportunity to the development of new types of block copolymers which can have advantages over conventional TPEs. Acrylic block copolymers (BCP) have superior resistance to weatherability, oxidative/ozonolytic degradation and have much improved oil resistance properties. We have prepared different types of BCPs via transition metal catalyzed CRP, widely known as ATRP using poly(methyl methacrylate) (PMMA) or poly(furfuryl methacrylate) (PFMA) as hard segment and poly(hexyl acrylate) or poly(2-ethyl hexyl acrylate) as the soft segment. These BCPs were characterized by NMR, GPC, DSC and DMA analyses. Their morphology was analyzed by AFM, TEM and SAXS analyses. Interestingly, BCPs having furfuryl functionality were modified via Diels-Alder “click” reaction using bismaleimides. These modified BCPs showed self-healing characteristics. We have also modified SBS BCPs via thiol-ene reaction to improve their properties.