The microstructure and texture evolution of Ni-5 at%W (Ni5W) alloy substrates were investigated by in situ tensile testing along the rolling direction (RD), transverse direction (TD), and at 45° to the RD (45°-RD), as well as by electron backscatter diffraction characterization. The tensile stress direction had a significant influence on the texture evolution. The cubic texture in the Ni-5 at%W alloy exhibited severe degradation when the tensile angle was 45°-RD. In contrast, the cubic texture was relatively stable under high deformation along the RD or TD. It was found that the slip line system in the 45°-RD specimen was the key to the contrasting behavior. The effect of the tensile testing angle on the cubic texture evolution for Ni–W substrates was investigated, and the corresponding effect on the superconducting properties of coated materials was studied.