Microstructure and mechanical properties of NiAlV alloys of the composition belonging to the pseudo-binary Ni3Al-Ni3V cross-section were investigated. The samples were prepared by the cold crucible levitation melting (CCLM) and by re-melting and crystallizing in the small volume copper mould. The phase composition of the samples, with should result from the eutectoidal decomposition was not found. Instead the Ni3(Al,V) and Ni(Al,V) solid solution or seldom disordered solid solution were retained due to the relatively high cooling rates. In the compression test the NiAlV alloys crystallized in the copper mould revealed high ductility and strength.