We investigated the influence of free-standing GaN (FS-GaN) substrates on the performance of ultraviolet light-emitting-diodes (UV-LEDs) grown on top by atmospheric pressure metal-organic chemical vapor deposition. High-resolution double-crystal x-ray diffraction (HRDCXD) analysis demonstrated high-order satellite peaks and clear fringes between them for UV-LEDs grown on the FS-GaN substrate, from which the interface roughness was estimated. In addition, the full width at half maximum of the HRDCXD rocking curve in the (0002) and the (101¯2) reflections were reduced to below 90 arc sec. The Raman results indicated that the GaN-based epilayer of strain free was grown. Additionally, the effect of the FS-GaN substrate on the crystal quality of the UV-LEDs was examined in detail by transmission electron microscopy (TEM). The TEM characterizations revealed no defects and V-pits were found in the scanned area. Based on the results mentioned above, the light output power of UV-LEDs on the FS-GaN substrate can be enhanced drastically by 80% and 90% at 20 and 100 mA, respectively. Furthermore, an ultralow efficiency degradation of about 3% can be obtained for the UV-LEDs on the FS-GaN substrate at a high injection current. The use of an FS-GaN substrate is suggested to be effective for improving the emission efficiency and droop of UV-LEDs grown thereon.