An appropriate modification technique for silk materials is needed to effectively improve their physical properties for specific applications. A telechelic-type polyalanine (T-polyA) was synthesized by papain-catalyzed polymerization as a novel reinforcing agent for silk materials. A silk fibroin obtained from Bombyx mori was homogeneously doped with T-polyA, and casting a solution of silk fibroin and T-polyA in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) resulted in a robust and transparent film. Tensile deformation studies of the silk composite film containing T-polyA with prestretching revealed that the tensile strength and toughness were enhanced relative to those of a silk-only film. To determine the capability of T-polyA to reinforce the tensile property of silk films, the secondary structure in the silk composite film was characterized by wide-angle X-ray diffraction (WAXD) analysis. Antiparallel β-sheet structures of T-polyA and GAGAGS motifs of silk fibroin formed independently in the prestretched composite film. In addition, measuring the tensile deformation and performing WAXD analysis simultaneously demonstrated that the β-sheet structures of both T-polyA and the silk fibroin were aligned along the stretching direction and that T-polyA had no significant effect on the final morphology of the silk crystal domains. The silk film was toughened by the addition of T-polyA because of the generation of the T-polyA β-sheet in the amorphous region of the composite film. This work provides novel insight into the design and development of tough silk materials with controlled and aligned β-sheet structures.