A Ni-1.76 wt%W alloy liner for shaped charge was prepared by means of electrodeposition. The microstructure of the as-deposited and as-annealed alloys was examined by X-ray diffraction, transmission electron microscope and Auger electron spectroscopy technique. Mechanical properties of alloys were evaluated by tensile tests. The results demonstrate that the electrodeposited alloy has high strength, fine grains and a strong (111) texture. The prepared Ni-W alloy still has fcc structure and W is solid solutioned in Ni lattice. By annealing at 300 °C, abnormal grain growth appears in the sample. (111) texture weakens and (220) texture tends to appear. At 500 °C, sulfur segregation at grain boundary has a detrimental effect on the tensile properties of the alloy.