In this work, a new method based on nanoscaled Ni-P alloy coating on carbon fiber surfaces is proposed for the improvement of interfacial properties between fibers and epoxy matrix in a composite system. Fiber surfaces and the mechanical interfacial properties of composites were characterized by atomic absorption spectrophotometer (AAS), scanning electron microscopy (SEM), X-ray photoelectron spectrometry (XPS), interlaminar shear strength (ILSS), and impact strength. Experimental results showed that the O-1s/C-1s ratio or Ni and P amounts had been increased as the electroless nickel plating proceeded; the ILSS had also been slightly improved. The impact properties were significantly improved in the presence of Ni-P alloy on carbon fiber surfaces, increasing the ductility of the composites. This was probably due to the effect of substituted Ni-P alloy, leading to an increase of the resistance to the deformation and the crack initiation of the epoxy system.