Nerve guidance conduits (NGCs) can provide suitable microenvironment for nerve repair and promote the proliferation and migration of Schwann cells (SCs). Thus, we developed nerve guidance conduits (NGCs) with polypyrrole-coated polycaprolactone nanoyarns (PPy-PCL-NYs) as fillers in this study. PCL-NYs with the oriented structure were prepared with a double-needle electrospinning system and then PPy was coated on PCL-NYs via the in situ chemical polymerization. Subsequently, PCL nanofibers were collected around nanoyarns by the conventional electrospinning process as the outer layer to obtain PPy-PCL-NY nerve guidance conduits (PPy-PCLNY NGCs). PPy-PCL-NYs were analyzed by SEM, FTIR and XPS. Results showed that PPy was homogeneously and uniformly deposited on the surface of PCL-NY. Strain-stress curves and the Young’s modulus of PPy-PCL-NYs were investigated compared with those of non-coated PCL-NYs. Studies on biocompatibility with SCs indicated that PPy-PCL-NY NGCs were more conducive to the proliferation of SCs than PCL-NY NGCs. In summary, PPy-PCL-NY NGCs show the promising potential for nerve tissue engineering repair and regeneration.