A 49.8 at.%Ti-50.2 at.%Ni shape memory alloy was applied to a current collector of positive electrode for lithium/sulfur (Li/S) battery. Flexible austenitic phase having pseudoelasticity dominated in the Ti-Ni current collector at room temperature. In the discharge curve, two plateau regions due to the lithium polysulfide (Li2Sn) and the lithium sulfide (Li2S) were obviously observed. The initial discharge capacity was 1068 mAh/g for Li/S cell with the Al current collector, and that of the cell with the Ti-Ni current collector reached 1140 mAh/g. A little bit of declined cycle performance was associated with decreased sulfur utilization owing to a reaction with dissolved Ti and Ni elements. Compared with the Al current collector used commercially, the Ti-Ni alloy with pseudoelasticity was more suitable to apply for the current collector of Li/S battery.