The synthesis of a family of polymer stars with arms of varied tacticities is discussed. The effect of polymer tacticity on the physical properties of these polymer stars is dramatic. Dipentaerythritol cores support six poly(lactic acid) arms. Lewis acidic tin and/or aluminum catalysts control the polymerization to afford polymer stars of variable tacticity. Analysis of these polymers by 1H NMR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and differential scanning calorimetry reveals the effects of tacticity control on the physical properties of the polymer stars. Hydrolytic decomposition studies suggest that the degradation profile of a polymer star may also be tuned by stereochemical control. Differences between isotactic samples derived from rac-lactide and L-lactide are heightened by longer arms of 50 and 100 monomer units. Control of polymer isospecificity shows that a similar to 70% isotacticity bias is necessary to induce crystallinity and alter the thermal and degradation properties of the material. Above 70% isotacticity, the degradation properties and thermal transitions can be further tuned across a relatively wide range. This technique allows for significant tunability to the physical properties of aliphatic polyester polymer stars. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012