The invention provides an ultraviolet light-emitting diode (LED) epitaxial structure. The epitaxial structure sequentially comprises an AlN Buffer layer, a high-temperature UGaN layer, a composite N-type GaN layer, a multi-quantum well (MQW) structure, an active region light-emitting quantum-well layer, an electron blocking layer (EBL) and a P-type GaN layer from bottom to top, wherein the active region light-emitting quantum-well layer comprises n layers of In<x>Ga<1-x>N/Al<y>Ga<1-y>N multi-quantum wells, each layer of In<x>Ga<1-x>N/Al<y>Ga<1-y>N multi-quantum well comprises a main barrier and a movable barrier, the movable barrier is embedded into the main barrier, the main barrier comprises Al<y>Ga<1-y>N, the height of the main barrier is gradiently increased with the increase of Al constituent, the movable barrier comprises GaN, and the thickness of each layer of movable barrier is 1-20 nanometers. By the ultraviolet LED epitaxial structure and a growth method thereof, the stress in the quantum wells is reduced, the hole injection efficiency is improved, electrons of an active layer is prevented from overflowing, and the carrier recombination probability and the internal quantum efficiency of an ultraviolet LED are improved.