A series of cast Ni3Al-base alloys with the addition of alloying elements, such as Hf, Zr, Ti, Nb etc., have been studied, in which the total amount of Al and alloying elements substituting for Al was controlled in the range of 18 to 23 at%. It was found the alloying elements change remarkably the morphology, distribution and amount of γ phase as well as the morphology and size of primary γ′ intermetallic compound. The size of primary γ′ can be decreased to micron order. The brittle γ′-γ′ boundary (refer to primary γ′) can be substituted by tough γ′-γ-γ′ boundary. As a result, the mechanical properties of the cast Ni3Al-base alloys, especially high temperature ductility, can be enhanced. In addition, the effect of Cr is discussed when tested in air environment, and considered that chromium addition is not very effective to improve the high temperature embrittlement.