A method to overcome the brittleness of poly (L.-lactic acid) (PLLA) by kinetically trapping a continuous low T-g amorphous phase is presented. This morphology is accomplished by exploiting the significant difference in the crystallization temperatures of PLLA vs its stereocomplex with the poly (D-lactic acid) (PDLA) isomer. In our studies, the D isomer is the end block of a triblock copolymer with a configuration of the form PDLAn -Soft Blockm-PDLAn. As demonstrated in this study, when blended with PLLA, the obtained morphology, and improvement in the sample toughness and flexibility, strongly depend on the miscibility of the midblock in the triblock copolymer with the matrix PLLA. The difference in the chemical nature of the midblock clearly affected the stereocomplex crystallization between the PDLA end blocks, the PLLA matrix polymer, and the morphology formed. It is found that the miscible midblock gives rise to a soft continuous amorphous phase while in the case of an immiscible midblock, a glassy phase separated amorphous phase is formed. Dramatically different physical properties can be obtained for various PLLA/triblock copolymer blends giving access to tough, yet flexible, semicrystalline PLLA blends. (C) 2012 Elsevier Ltd. All rights reserved.