To enhance the reinforcement effects of regenerated cellulose nanofibers (RC-NF) in poly(ε-caprolactone) (PCL), we synthesized RC-NF-3-aminopropyltriethoxysilane (APS), the surface-modified RC-NF by APS. The RC-NF were fabricated by the saponification of electrospun cellulose-acetate nanofibers. The surface modification by APS was confirmed by the X-ray photoelectron spectroscopy (XPS). To enhance the mechanical property of PCL, the RC-NF and the RC-NF-APS were separately compounded into PCL by compression molding. It was found that, when the fiber concentration of RC-NF-APS was 17 wt %, the Young's modulus at room temperature increased from 698.0 to 744.7 MPa, whereas the storage modulus at 55 C almost increased from 180 to 220 MPa. The micrographs of the fracture surface of the composites revealed that the surface modification prevented the pull-out of RC-NF from PCL. It was concluded that the mechanical properties of the composites were enhanced due to the improvement of the compatibility between RC-NF and PCL by the surface modification with APS.