A molecularly-ordered thin film of vacuum deposited 1-TNATA(4,4 ',4 ''-tris (N-(1-naphthyl)-N-phenylamino)triphenylamine) as a hole injection layer (HIL) is placed between indium tin oxide (ITO) electrode and a hole transporting layer (HTL) in multi-layered organic electroluminescence (EL) diodes. The molecular ordering of 1-TNATA thin film was obtained by thermal annealing and electromagnetic field after vacuum deposition and the film was investigated by the Raman spectra, XRD, and AFM. It was found that the current density-voltage (J-V) and luminance-voltage (L-V) characteristics of the multi-layered diodes were improved due to the ordering of 1-TNATA molecules, which could enhance the charge carrier mobility and luminance efficiency among the organic molecules in the molecularly-ordered film.