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Poly(L‐lactic acid) (PLLA) with high ductility and transparence is fabricated by a blending tiny amount of polyvinylidene fluoride (PVDF) and reactive comb compatibilizers (RCC). Upon blending, the reaction between terminal carboxyl groups in PLLA and expoxy groups in RCC produces graft copolymer (PLLA‐g‐poly(methyl methacrylate) (PMMA)), which locates at the PVDF/PLLA interface due to the balanced stress on two sides. On the one hand, the PVDF domain size decreases remarkably with the help of compatibilization, accounting for the excellent transparence. On the other hand, the interface is enhanced significantly, resulting in an activated PLLA layer surrounding PVDF domains. The thickness exhibits higher magnitude because of the high molecular weight of grafted PLLA (relative to premade compatibilizers). During uniaxial tension, the activated PLLA layers (in addition to PVDF) can cause effective energy absorption and dissipation in the case of percolation of them, which is the reason for the better ductility. These results provide an efficient strategy to improve the ductility and transparence simultaneously. [ABSTRACT FROM AUTHOR]