The electrical and structural properties of V/Al-based n-contacts on n‐AlxGa1?xN with an Al mole fraction x ranging from x=0.75 to x=0.95 are investigated. Ohmic n-contacts are obtained up to x=0.75 with a contact resistivity of 5.7×10?4Ω·cm2 whereas for higher Al mole fraction the IV characteristics are rectifying. Transmission electron microscopy reveals a thin crystalline AlN layer formed at the metal/semiconductor interface upon thermal annealing. Compositional analysis confirmed an Al enrichment at the interface. The interfacial nitride-based layer in n-contacts on n‐Al0.9Ga0.1N is partly amorphous and heavily contaminated by oxygen. The role and resulting limitations of Al in the metal stack for n-contacts on n-AlGaN with very high Al mole fraction are discussed. Finally, ultraviolet C (UVC) LEDs grown on n‐Al0.87Ga0.13N and emitting at 232 nm are fabricated with an operating voltage of 7.3 V and an emission power of 120 μW at 20 mA in cw operation.