Poly(lactide) (PLA) has received tremendous attention recently from researchers and industrialists due to its ability to solve environmental problems related to plastic pollution. However, PLA's brittleness, poor thermal stability, low elongation at break, and poor melt processing prevent its use in a broader spectrum of applications. Herein, we produced a very tough and thermally more stable PLA stereocomplex by simply mixing PLA with organoalkoxysilane. The stereocomplex PLA/silane (sc-PLA–silane) composite was prepared by simple mixing of three types of organoalkoxysilanes in sc-PLA followed by in situ formation of a silane-based rubbery core with a cross-linked PLA shell. Mechanical and thermal properties were improved by stereocomplexation of PLA with a small amount (1–5 wt%) of PLA-grafted silanes. The addition of organoalkoxysilane with different functional groups resulted in a plasticizer of rubbery silica-PLA core–shell gel through in situ condensation and grafting of long PLA chains at the interface between the stereocomplex and silane particles. The results revealed that the toughness of sc-PLA was improved dramatically with only a small addition (only 2.5%) of 3-(triethoxysilyl)propyl isocyanate (ICPTES). The morphology and mechanical and thermal properties of the toughened stereocomplex films were characterized. The results revealed that elongation at break was increased from 16% to 120%, while other mechanical properties such as tensile strength and modulus were retained. Surface analysis confirmed that this toughness was achieved by formation of a silica-PLA core–shell gel. The mechanical properties of PLA were improved without any significant reduction in modulus and tensile strength using this simple methodology.