We have designed a pathway for controlling the critical micelle concentration and micelle size of polyester-based systems. This was achieved by creating an array of different copolymers with semicrystalline or amorphous hydrophobic blocks. The hydrophobic block was constructed through ring-opening polymerization of ε-caprolactone, L-lactide, and ε-decalactone, either as homopolymers or random copolymers, using PEG as both the initiator and the hydrophilic block. Micelles formed with amorphous cores exhibited considerably higher critical micelle concentrations than those with semicrystalline cores. Micelles with amorphous cores also became larger in size with an increased molecular weight of the hydrophobic bock, in contrast to micelles with semicrystalline cores, which displayed the opposite behavior. Hence, core crystallinity was found to be a potent tool for tailoring micelle properties and thereby facilitating the optimization of drug delivery systems. The introduction of PEG-PεDL also proved to be a valuable asset in the tuning of micelle properties.