Monodisperse sub-2-nm EuOF nanowires were obtained by manipulating the fluorophilicity between crystalline seeds and capping surfactant molecules during the thermolysis of Eu(CF3COO)(3) in oleic acid (OA) and oleylamine (OM). The uniform EuOF nanowires can self-organize on substrates to form parallel aligned superstructures and display strong Eu(3+)red emissions with high quantum yields of 65% under the UV light excitations due to the presence of dense surface Eu3+ sites in the ultrathin nanowires as well as the passivation of the surface defects by the capping ligands.