Intermetallic alloys and compounds have attractive properties as high temperature structural materials. A dual two-phase Ni_3Al-Ni_3V intermetallic alloy with a nominal composition of Ni 75.0 Al 7.5 Vl 5.0 Nb 2.5(at%) doped with 50 mass ppm boron was formed by low pressure plasma spray process using atomized powder. The dual two-phase and intermetallic alloy whose microstructure exhibits the cuboidal primary Ni_3Al phase and the surrounding channel region composed of Ni_3Al and Ni_3V phases, and contains neither voids nor intermediate products were obtained by heat treatment after spraying. Relationships between the microstructures of the coatings and conditions of spray were discussed.