Inspired by the curved branches of fractal trees, hooked Ni–Fe fibers were grown in situ in Ni–Fe composite coatings on a spheroidal graphite cast iron substrate. These hooked Ni–Fe fibers exhibited inclination angles of about 39°, which was in accordance with the theoretical prediction of 37°. Ni–Fe nanostructures self-assembled to form dendrites and evolved into hooked fibers by an oriented attachment reaction. The orientation rotation of Ni–Fe nanostructures played an important role in the growth of curved hooked Ni–Fe fibers. During sliding wear tests, the volume loss of the spheroidal graphite cast iron substrate was 2.2 times as large as that of the Ni–Fe coating reinforced by hooked fibers. The good load-transferring ability of hooked Ni–Fe fibers led to an improvement in their wear properties during wear tests.