Deep-blue organic light-emitting diodes (OLEDs) with nearly 5% external quantum efficiency were demonstrated using a 1,4-(dinaphthalen-2-yl)-naphthalene (DNN) host. The 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl (BCzVBi) dopant that was used in this experiment effectively accepted energy from the DNN host via Förster energy transfer because the photoluminescence spectrum of the DNN host showed better spectra overlap with the ultraviolet-visible (UV-vis) absorption spectrum of the BCzVBi dopant than the photoluminescence spectrum of the 2-methyl-9,10-bis(naphthalen-2-yl)anthracene host did. Moreover, the DNN host had a higher energy bandgap (3.5 eV) than the BCzVBi dopant did (3.0 eV), while the MADN host had the same energy bandgap as the BCzVBi dopant. The optimized deep-blue device also had ETL of bis-(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium which showed smoother sigma of 0.6 nm and higher Tg of 92 degrees than those of 4,7-diphenyl-1,10-phenanthroline (14.8 nm and 62 degrees C). The deep-blue device exhibited a peak current efficiency of 5.68 cd/A, a peak external quantum efficiency of 4.89%, and Commission Internationale d' Eclairage coordinates of (0.15, 0.13).