Bi/BiSb superlattice nanowires (SLNWs) with a controllable and very small bilayer thickness and a sharp segment interface were grown by adopting a charge-controlled pulse electrodeposition. The deposition parameters were optimized to ensure an epitaxial growth of the SLNWs with a preferential orientation. The segment length and bilayer thickness of the SLNWs can be controlled simply by changing the modulating time, and the consistency of the segment length can be well maintained by our approach. The Bravais law in the electrodeposited nanowires is verified by the SLNW structure. The current-voltage measurement shows that the SLNWs have good electrical conductance, particularly those with a smaller bilayer thickness. The Bi/BiSb SLNWs might have excellent thermoelectric performances.