Semiconductor nanowires (NWs) composed of cadmium selenide (CdSe) have been directly grown on transparent conductive substrates via the solution-liquid-solid (SLS) approach using electrodeposited bismuth nanoparticles (Bi NPs) as catalyst. Bi NPs were fabricated on indium tin oxide (ITO) surfaces from a bismuth trichloride solution using potentiostatic double-pulse techniques. The size and density of electrodeposited Bi NPs were controlled by the pulse parameters. Since the NW diameter is governed by the dimension of the Bi catalyst, the electrodeposition is a reliable method to synthesize nanowires directly on substrates with a desired size and density. We show that the density can be adjusted from individual NWs on several square micrometer to very dense NW networks. The diameter can be controlled between thick nanowires above 100 nm to very thin NW of 7 nm in diameter, which is well below the respective exciton dimension. Hence, especially the thinnest NWs exhibit diameter-dependent photoluminescence energies as a result of quantum confinement effects in the radial dimension.