A well-defined series of nine poly(L-lactide)-b- (2-dimethylaminoethyl methacrylate) (PLLA-b-PDMAEMA) linear diblock copolymers with low polydispersity were prepared by ring-opening polymerization of LLA using 4-isopropylbenzyl alcohol and tin octoate as the initiating system, conversion of the OH-terminated PLLA into Br-terminated macroinitiators (S, 13, and 19 kg/mol), followed by atom transfer radical polymerization of DMAEMA (to obtain one-half, equal, and twice the molecular weight of each PLLA block). Compositional analysis and molecular weight characterization were done using NMR, SEC-LS, TGA, polarimetry, and PDMAEMA quaternization/precipitation to test for residual PLLA homopolymer. DSC investigations indicate that low molecular weight amorphous PLLA or PDMAEMA blocks (less than or equal to ca. 5000 g/mol) are miscible in the second block. Compared to the parent PLLA homopolymers, PLLA crystallization in the block copolymers is significantly retarded, whereas the degree of crystallinity is only mildly affected and melting points are reduced only for the low molecular weight miscible blocks.