A small addition of boron is suggested to increase the ductility of the polycrystalline Ni3Al when the Al content is less than 25 at.%. Both metallographic and x-ray investigation have shown the alloys of Ni3Al (24 at.% Al) containing 0.20, 0.42, 0.79, 0.98, and 1.22 at.% B to be of single phase and that of 1.76 at.% B to be of two phase. With the addition of boron, the lattice parameter of the Ni3Al phase is found to increase. Microhardness measurements indicate that initially the hardness decreases for the alloy of 0.20 at.% B, while for the rest of the single phase alloys the hardness is found to increase with further addition of boron. The addition of boron increases the deformation stacking fault probability value except for the alloy with 0.20 at.% B.