This study explores the novel approach of interface-crystallization-induced compatibilization (ICIC) via stereocomplexation as a promising method to improve the interfacial strength in thermodynamically immiscible polymers. Herein, two distinct reactive interfacial compatibilizers, poly(styrene-co-glycidyl methacrylate)-graft-poly(l-lactic acid) (SAL) and poly(styrene-co-glycidyl methacrylate)-graft-poly(d-lactic acid) (SAD) are synthesized via reactive melt blending in an integrated grafting and blending process. This approach is demonstrated to enhance the interfacial strength of immiscible polyvinylidene fluoride/poly l-lactic acid (PVDF/PLLA) 50/50 blends via ICIC. IR nanoimaging indicates a cocontinuous morphology in the blends. The blend compatibilized with SAD exhibits a higher storage modulus, as unveiled by small amplitude oscillatory shear (SAOS) in the melt state at a temperature below the melting temperature of the stereocomplex (SC) crystals and by DMTA measurements in the solid state. This increase is attributed to the formation of a 200–300 nm thick rigid interfacial SC crystalline layer that is directly visible using AFM imaging and chemically characterized via IR nanospectroscopy. This ICIC also results in a significant toughening of the blend, with the elongation at break increasing more than 20-fold. Moreover, the fracture toughness factor obtained from single edge-notch bending (SENB) tests is doubled with ICIC as compared to the uncompatibilized blend, indicating the strong crack-resistance capability as a result of ICIC. This improvement is also evident in SEM images, where thinner and longer fibrillation is observed on the fractured surface in the presence of ICIC.