A series of polylactide/poly(ethylene glycol) (PLA/PEG) block copolymers were synthesized by ring-opening polymerization of L- or D-lactide in the presence of mono- or di-hydroxyl PEG. The effects of stereocomplexation on the physicochemical behavior of PLA/PEG copolymers in aqueous solution were investigated by varying the degree of stereocomplexation or PLLA/PEG to PDLA/PEG ratio. In mixture solutions of insoluble and soluble copolymers, stereocomplexation strongly affects the solubility of the copolymers. In mixture solutions of soluble copolymers, both the size and aggregation number (Nagg) of the aggregates vary as a function of the degree of stereocomplexation. It is suggested that the size variation of the aggregates with increasing the degree of stereocomplexation is dependent on Nagg changes which are determined by two effects: the self-adjusting of the aggregates so as to minimize the free energy and thus to increase the Nagg, and the kinetics of aggregation which tend to form more aggregates and thus to decrease the Nagg. Combination of the two opposite effects well explains the diverse variations of Nagg and size of the aggregates as a function of the degree of stereocomplexation. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012