Radial block copolymers characterized by the formulas: (1) (pS-pI).sub.n X and (2) (pS-pI-pB).sub.n X where pS is polystyrene, pI is polyisoprene, pB is butadiene, X is a residue of a multifunctional coupling agent used in the production of the radial block copolymer, and n is a number greater than 2 representative of the number of branches appended to X; hot-melt adhesive compositions constituted of said radial block copolymers, and articles of manufacture produced therefrom. These copolymers possess blocks of high average molecular weight polystyrene (10,000 to 25,000) and an overall average molecular weight (90,000 to 380,000) such that when blended in requisite proportions with a compatible tackifier resin, preferably also a secondary tackifying resin or plasticizing oil, and stabilizer, superior hot-melt adhesive compositions can be formed. The hot-melt adhesive compositions possess, inter alia, superior heat resistance, superior static time to failure with low viscosity, good peel adhesion, good tack, and high ability to bond to a polyethylene or polypropylene substrate at temperatures below that which may damage the substrate.