Spontaneous stereocomplex aggregation of diblock poly(styrene)-b-poly(L-lactide) PS-b-PLLA/poly(D-lactide) PDLA pairs has been investigated under ambient temperature in tetrahydrofuran solution. First, diblock PS260-b-PLLA(165) and PS260-b-PDLA(162) bearing similar lengths of respective PLLA and PDLA blocks were synthesized through controlled atom-transfer radical polymerization of styrene, and a subsequent living ring-opening polymerization of optically pure lactides, and their structures were further characterized by nuclear magnetic resonance spectroscopy (NMR) and gel-permeation chromatography (GPC). Subsequently, new enantiomeric poly(D-lactide) stabilized core-shell fluorescent CdSe quantum dots (CdSe/PDLA QD) were designed and prepared as sensitive fluorescence labels to shed new lights on the spontaneous stereocomplex aggregation in THF, which was mediated by stereocomplexation of the PLLA and PDLA chains. Upon simply mixing two individual THF solution of diblock PS260-b-PLLA(165) and HO-PDLA(30)-SH, spontaneous stereocomplex aggregation was studied, and the aggregated uniform spherical particles were observed by scanning electronic microscopy (SEM) to exhibit average particle diameters of 2.0 mu m. Finally, utilizing the prepared CdSe/PDLA QDs as new fluorescent labels, morphologies of the spontaneous aggregates by new diblock PS260-b-PLLA(165)/HO-PDLA(30)-SH pair were for the first time directly visualized by a confocal laser scanning fluorescence microscopy (CLSFM). These results might suggest alternative ways to simply prepare functional fluorescent particles with tunable diameter sizes and would be helpful to understand the mechanism of stereocomplex particle aggregation. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1393-1.405, 2009