Benefiting from both one-dimensional (1D) morphology and alloy composition, metal alloy nanowires have been exploited as advanced electrocatalysts in various electrochemical processes. In this review, the synthesis approaches for metal alloy nanowires are classified into two categories: direct syntheses and syntheses based on preformed 1D nanostructures. Ligand systems that are of critical importance to the formation of alloy nanowires are summarized and reviewed, together with the strategies imposed to achieve the co-reduction of different metals. Meanwhile, different scenarios that form alloy nanowires from pre-synthesized 1D nanostructures are compared and contrasted. In addition, the characterization and electrocatalytic applications of metal alloy nanowires are briefly discussed.