In the stereocomplex between enantiomeric poly(l-lactide) (l-PLA) and poly(d-lactide), crystallites formed as a result of stereocomplexation, equimolar l- and d-lactide unit sequences are packed side by side. The stereocomplex exhibits a melting temperature higher by about 50 °C than that of each homopolymer. In this study, we attempt to obtain further insight into the stereocomplex-induced surface structure of enantiomeric PLA blend films. The design of the blend systems is based on principles of surface segregation of multicomponent polymeric systems with a low surface energy, triblock copolymer (l-PLA-b-PDMS-b-l-PLA) of l-PLA and poly-(dimethyl siloxane). (l-PLA-b-PDMS-b-l-PLA/l-PLA) blend films showed the surface segregation of PDMS, regardless of blend composition while the surface composition of PDMS in the (l-PLA-b-PDMS-b-l-PLA/d-PLA) blend films was strongly depended on blend composition or a degree of complexation. These results are likely due to strong interaction between d- and l-lactide unit sequences, which prevents the surface segregation of PDMS.