Three linear pentablock quintopolymers (I-SIDMV), where S is polystyrene (PS), I polyisoprene-1,4 (PI), D poly(dimethylsiloxane) (PDMS), M poly(tert-butyl metbacrylate) (PtBuM), and V poly(2-vinylpyridine) (P2VP), were synthesized by anionic polymerization high vacuum techniques. The approach involves the following: (a) The synthesis of living triblock terpolymer PS-b-PI-b-PDMSLi and diblock copolymer P2VP-b-PtBuMK by sequential polymerizations of the corresponding monomers with sec-BuLi and benzyl potassium, respectively; and (b) The selective linking of the living triblock terpolymer with the chlorosilane group of 2-(chloromethylphenyl)ethyldimethylehlorosilane (CMPDMS), followed by linking of the living block copolymer with the remaining chloromethyl group of CMPDMS. Molecular characterization carried out by size exclusion chromatography, membrane osmometry, solution (in CDCl3 or d(8)-toluene) and solid-state H-1-NMR spectroscopy indicated a high degree of molecular and compositional homogeneity. Differential scanning calorimetry results on the precursors and final polymers were discussed. (c) 2008 Wiley Periodicals, Inc.