Semiconductor CdSe nanowires (NWs) can serve as model systems for investigating the physical properties of one-dimensional (1D) nanostructures and have great potential for applications in electronics and photonic nanodevices. With numerous attractions arisen from their physical properties, CdSe NWs have been synthesized by vapor-liquid-solid (VLS) methods, but they have some limitations of high reaction temperature and low production. Here, we synthesized CdSe NWs via the solution-liquid-solid (SLS) mechanisms using bismuth (Bi) covered substrates as a low-melting point catalyst and compared the products after injecting identical amount of Se and different amount of tributylphosphine (TBP). CdSe NWs have similar diameters but longer lengths with decreasing TBP, so we proposed the role of TBP as a solvent and capping agent of Se.