Well-defined multiarmed star random and block copolymers of e-caprolactone with L-lactide with controlled molecular weights, low polydispersities, and precise numbers of arms were synthesized by the ring-opening polymerization of respective cyclic ester monomers. The polymers were characterized by 1 H-NMR and 13 C-NMR to determine their chemical composition, molecular structure, degree of randomness, and proof of block copolymer formation. Gel permeation chromatography was used to establish the degree of branching. Star-branched random copolymers exhibited lower glass-transition temperatures (T g 's) compared to a linear random copolymer. When the star random copolymers were melt-blended with poly(L-lactic acid) (PLA), we observed that the elongation of the blend increased with the number of arms of the copolymer. Six-armed block copolymers, which exhibited higher T g 's, caused the maximum improvement in elongation. In all cases, improvements in the elongation were achieved with no loss of stiffness in the PLA blends.