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 presented. Dipentaerythritol cores support six poly(lactic acid) (PLA) arms. Lewis acidic tin and aluminum catalysts control the polymerization to afford polymer stars of variable tacticity. The analysis of these polymers by 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. Preliminary decomposition studies suggest that the biodegradation profile of a polymer star may also be tuned by stereochemical control. This is the first systematic altering of tacticity in PLA polymer stars, showing that polymer tacticity can have a great impact on star properties.