A new method for surface modification based on the arc surface alloying has been proposed and its feasibility has been investigated performing niobium aluminide coating on a niobium base metal. When tungsten arc was used to melt an aluminum plate placed on a niobium block, the niobium surface was also melted and a melt pool of an Al-Nb binary alloy was formed on the niobium block. The melt pool solidified into niobium aluminides on the surface of the niobium block, forming a thick NbAl3 layer on the top surface of the coating layer. When an Al-Si alloy plate was used instead of the aluminum plate, a niobium aluminosilicide layer was formed on the niobium block.