Anionic random and block. copolymerization of isobornyl methacrylate (IBMA) and methyl methacrylate (MMA) has been studied in THF at -78 degrees C by using (1,1-diphenyl-3,3-dimethylbutyl)lithium (DDBLi) as initiator in the presence of LiCl. The random copolymerization of MMA and IBMA has also been carried out at 0 degrees C, all the other conditions being kept unchanged. Poly[poly(IBMA)-b-poly(BD)b-poly(IBMA)] (IBI), poly[poly(IBMA-co-MMA)-b-poly(BD)-b-poly(MMA-co-IBMA)] (I/MBM/I), and poly[poly(IBMA)-b-poly(MMA)-b-poly(BD)-b-poly(MMA)-b-poly(IBMA)] (IMBMI) block copolymers have been synthesized by sequential anionic polymerization of butadiene, MMA, and IBMA initiated by the m-diisopropenylbenzene (m-DIB)/tert-butyllithium (t-BuLi) diadduct. These block copolymers of a monomodal and narrow molecular weight distribution ((M) over bar(w)/(M) over bar(n) = 1.1) have been analyzed by size exclusion chromatography (SEC), NMR, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy(TEM). Stereocomplexation of IMBMA and I/MBM/I with iPMMA has also been studied by DSC. Although IBI triblock copolymers show a lamellar morphology even for relatively low hard block content (33 wt %), cylindrical and lamellar morphologies have been observed for the other block copolymers under consideration. These new block copolymers exhibit high ultimate tensile strength (30 MPa), elongation at break (1000%), and upper service temperature (140-200 degrees C).