Graphite-nanoplatelet (GNP)-decorated polymer nanofiber composites with hierarchical structures were fabricated by the combination of electrospinning and ultrasonication. It was found that GNPs could be well attached or embedded onto the nanofibers when their size was comparable to the nanofiber diameter. X-ray diffraction results indicated that ultrasonic treatment exerted no influence on the carbon crystal layer spacing. Fourier transform infrared spectra and Raman spectroscopy revealed the existence of interfacial interaction between GNPs and polyurethane nanofibers. The prepared nanofiber composite showed enhanced thermal stability and hardness, which originated from uniform dispersion of GNPs as well as strong interaction between GNPs and the nanofibers. The electrical conductivity was significantly improved, derived from the formation of a conductive percolation network in the nanofiber composite. During ultrasonication, cavitation bubbles may be formed in liquid, and microjets and shock waves were created near the GNP surface after collapse of the bubbles. These jets, causing sintering of GNPs, pushed GNPs toward the nanofiber surface at very high speeds. When the fast-moving GNPs hit the nanofiber surface, interfacial collision between GNPs and the nanofibers occurs, the nanofiber may experience partial softening or even melting at the impact sites, and then GNPs could be uniformly anchored onto the nanofibers. This method opens a new door for harvesting GNP-based nanofiber composites with improved material properties.