Poly(lactic acid)-block-poly(ethylene glycol) copolymers (PLA-b-PEG) featuring varying tacticities (atactic, heterotactic, isotactic) in the PLA block were synthesized and investigated for their micellar stability, degradation, and thermal properties. Utilizing tin(II) bis(2-ethylhexanoate), aluminum salan, and aluminum salen catalysts, the copolymers were synthesized through the ring-opening polymerization of d-, l-, rac-, or a blend of l- and rac-lactide using monomethoxy-poly(ethylene glycol) as a macroinitiator. The critical micelle concentration, which reflects the micellar stability, was probed using a fluorescence spectroscopic method with pyrene as the probe. The copolymers were degraded in a methanolic solution of 1,5,7-triaza-bicyclo[4.4.0]dec-5-ene and the degradation was measured by H-1 NMR spectroscopic and gel permeation chromatographic analyses. Differential scanning calorimetry and thermogravimetric analysis provided information on the thermal properties of the copolymers. Atactic and heterotactic microstructures in the PLA block resulted in lower micellar stability, as well as faster degradation and shorter erosion time compared to polymers with high isotactic enchainment (P-m). By modification of the P-m, micellar stability, degradation, and erosion rates of the copolymers can be tuned to specific biomedical applications. Interestingly, while tin(II) bis(2-ethylhexanoate) and aluminum salan-catalyzed PLA-b-PEG copolymers exhibited similar micellization behavior, the aluminum salen-catalyzed PLA-b-PEG exhibited unique behavior at high micelle concentration in the presence of the pyrene probe. This unique behavior can be attributed to the disintegration of the micelles through the interactions of long isotactic stereoblock segments.