Epitaxially grown high crystalline quality InGaN/AlGaN multiple quantum structures on patterned sapphire with silica array (PSSA) have been successfully demonstrated. In comparison to conventional epilayers grown on patterned sapphire substrate (PSS), we observed a reduced threading dislocation density in the films grown on PSSA, attributing to the preferable vertical growth mode and reduced misfit at the coalescence boundary. Furthermore, a significant enhancement in light extraction efficiency can be achieved from InGaN/AlGaN-based ultraviolet light-emitting diodes (UVLEDs) built on PSSA owing to the large refractive index contrast between the epilayers and PSSA. More photons can escape from the top and bottom of the device, which was confirmed by numerically modeling light propagation within such device architecture. Benefiting from the reduced threading dislocation density and enhanced light extraction efficiency, the external quantum efficiency (EQE) of the fabricated UVLEDs on PSSA was more than two times higher than that of devices on the conventional flat sapphire substrate and it was additionally enhanced by 26.1% in comparison to the devices fabricated on PSS under an injection current of 150 mA. Therefore, the successful demonstration of UVLED on PSSA provides an unprecedented opportunity in achieving higher electroluminescence performance in future solid-state UV light sources. Display omitted •Patterned sapphire with silica array (PSSA) was demonstrated a prominent substrate for highly efficient UVLEDs.•AlGaN epilayers grown on PSSA showed preferable vertical growth mode and reduced misfit at coalescence boundary.•PSSA enlarged the index contrast between epilayer and substrate, which facilitated more efficient light extraction.