The microstructures and room temperature mechanical properties of melt spun Ni-34.6 at % Al annealed at 1523 K for 2 h and cooled at different rates were studied. The annealed microstructures and bend ductility were sensitive to the cooling rate. The distribution and relative content of gamma’ precipitation were important factors for enhancement of bend ductility of the annealed ribbon. The best bend ductility of the annealed ribbon reached 7.6%, which was considerably better than the as-melt spun ribbon. The emission and transmission of dislocations from ductile gamma’ into beta to satisfy the need of deformation compatibility played a key role in the improvement of the ductility.