Dual-phase Ni3Al-based alloys feature extensive applicability even under high-temperature conditions. We selectively modified the microstructure of a representative dual-phase Ni3Al-based alloy from equi-axed grains to unidirectional grains, using a kW-class high-power laser irradiation technique. On employing the laser probe to linearly scan the Ni-9 at.% Al-16 at.% V alloy specimen, the laser-irradiated region was partially molten and then immediately solidified from the two edges of the molten pool toward the center. Laser irradiation under low-speed scanning increased the molten pool width. The grains in the laser-irradiated region extended preferentially from the two edges toward the center; their crystal orientation was similar to adjacent substrate grains, suggesting epitaxial growth. Therefore, the unidirectional orientation of grains could be extended via wide-range scanning using laser irradiation. This suggests that the microstructure of the alloy can be selectively modified to unidirectional orientated grains by optimizing laser irradiation conditions, such as the power density, scanning speed, and scanning paths. The hardness of the laser-irradiated region decreased due to the phase transformation from the ordered Ni3Al and Ni3V phases to the disordered fcc phase. However, the hardness improved to a value comparable to that of the alloy subjected to heat treatment at 980 °C for 1 h.