Solution-processed near-infrared organic light-emitting diodes (NIR-OLEDs) with structure glass/indium–tin oxide/poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)/Er-complex/Ca/Al based on a novel Er(III) complex, [Er(tfnb)3(bipy)] (Htfnb = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione and bipy = 2,2′-bipyridine) have been manufactured and their properties have been studied. A complete quenching of the organic ligand visible emission is shown, and only the sensitized 1.5 μm electroluminesce from Er(III) results. From the electrical characteristic we present the mobility dependence on applied voltage using a numerical model, comparing it to poly(9,9-dioctylfluorene), a commercial semiconducting polymer with optical properties close to those of the molecular ligands. The synthesis of the novel complex together with a detailed analysis of its structure elucidated by XRD, 1H NMR, Raman, and Fourier-transform infrared spectroscopies is presented. A wide-ranging characterization of its photophysical properties in terms of absorption and steady and transient photoluminescence is used to investigate the energy-transfer process from the organic ligand to the central Er(III) ion.