In this work, we combine the catalytic growth and ligand control mechanisms to synthesize ultrathin/ultralong ZnSe nanowires (NWs). Ag2Se catalyst seeds initiate the NW growth and significantly cause the increase of the NW lengths up to several micrometers. The long-chain amine mixture of oleylamine and 1-dodecylamine acts as reaction medium and ligands (or surfactants) to control the sizes of Ag2Se seeds and ZnSe NWs within several nanometers (the mean diameter of NWs: similar to 5.5 nm). The microstructure studies by HRTEM reveal the presence of zinc blende (ZB)/wurtzite (W) alternations and a number of stacking faults and twins within individual ZnSe ultrathin NWs. These NWs exhibit optical quantum confinement effect due to the diameters smaller than the theoretical exciton Bohr diameter of bulk ZnSe. Raman spectrum and photoelectronic performance under white light illumination are also presented.