In the poly(lactic acid) family, poly(l-lactic acid) (PLLA), poly(d-lactic acid) (PDLA), and mesomeric poly(d,l-lactic acid) (mPLA) have the same chemical constituents but distinct configurations. It is well-known that PLLA and PDLA could crystallize to homocrystals individually (HCL and HCD) or form stereocomplex crystals (SC) together. But it remains a debated question whether poly(lactic acid) mixtures with different chiralities can phase separate in melt or in solutions. Here, we study the phase transitions of PLLA/mPLA and PLLA/PDLA in dichloromethane (DCM) solutions at double emulsion interfaces. We find that crystallization is dominant in the low-molecular-weight (M-W) mixtures, while liquid-liquid phase separation indeed occurs ahead of crystallization in the high-M-W mixtures. The PLLA/mPLA double emulsion droplets transform into a spindle-like shape when the homocrystallization of PLLA is dominant in the low-M-W region, while eyeball-like microcapsules form when phase separation is dominant in the high-M-W region. The PLLA/PDLA double emulsion droplets are solidified to spherical microcapsules with dense stereocomplex crystallites at low M(W)s, while the multiphase patchy microcapsules form by sequential liquid-liquid phase separation, stereocomplex crystallization, and homocrystallizations at high M(W)s. We quantify a very weak repulsive energy of 0.0050kT (kT is the thermal energy at room temperature) between the l- and d-segments and depict the complete phase diagrams to provide insight into the multiple phase transitions. This study quantifies the interaction of poly(lactic acid) mixtures and provides a design principle for taking advantage of chiral polymers to modulate the microcapsule structures and properties via phase transitions at the liquid-liquid interface.