A series of poly[methyl methacrylate (M)-b-styrene (S)-b-butadiene (B)-b-S-b-M], or MSBSM, pentablock copolymers have been successfully synthesized by sequential living anionic polymerization initiated with the diadduct of tert-butyllithium (t-BuLi) onto m-diisopropenylbenzene (m-DIB) in a cyclohexane/diethyl ether mixture for the butadiene and styrene polymerization at room temperature and in a cyclohexane/THF mixture for the MMA polymerization at -78 degrees C. All the pentablock copolymers have a monomodal and narrow molecular weight distribution (MWMn < 1.20), and their weight composition varies from 11 to 55% M, 18 to 55% S, and 15 to 64% B. Toluene-cast films of these copolymers have been analyzed by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). All these materials show a phase separation of the soft B component from the hard S and M blocks, which cannot, however, be distinguished one from each other by DSC or DMA. Indeed, a single transition is observed for the binary hard phase at a temperature intermediate between the glass transition temperature of polystyrene (PS) and poly(methyl methacrylate) (PMMA). In addition to classical phase morphologies, such as cylindrical and lamellar phase organization, two nonclassical morphologies, i.e., catenoid-lamellar and strut phase structures have been observed by TEM. The phase morphology strongly depends on the pentablock composition and any chemical modification of blocks. For instance, the cylindrical morphology, characteristic of an MSBSM copolymer containing equal amounts of hard and soft phases, is changed into a lamellar morphology upon hydrogenation of the B midblock. Copolymers of a relatively low hard phase content typically behave as thermoplastic elastomers of high ultimate tensile strength (ca. 30 MPa) and elongation at break (ca. 900%). These mechanical properties, however, depend on the casting solvent.