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An in situ reaction of two optoelectronically active organic ligands (anionic thenoyltrifluoroacetylacetone, tta−, and neutral triphenylphosphine oxide, tppo) with erbium(III) ion in the presence of a base yielded a new erbium complex, [Er(tta)3(tppo)]. The solid and solution structure of the complex was established by X-ray crystallography, NMR, ESI-MS, FTIR, TGA and Raman spectroscopy. They indicate that the Er(III) ion is coordinated to seven oxygen atoms of three tta ligands and one tppo ligand in a monocapped octahedral geometry. The Judd–Ofelt parameters of the complex were determined by a least squares fitting and dealt with its chemical structure. On UV excitation through ligand mediation, the complex shows the characteristic near-infrared emission of the corresponding Er(III) ion at 1534 nm. Furthermore, a near infra-red organic light emitting diode (NIR-OLED) was fabricated with structure: ITO/[N,N′-bis(naphthalen-2-yl)-N,N′-bis(phenyl)benzidine]/[Er(tta)3(tppo)]/[2,2′,2′′-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)]/LiF/Al. This device, with maximum applied voltage of 23 V, shows a total quenching of visible emission and electroluminescence in the C-band region (1534 nm) which is suitable for third communication window applications in fiber optics. Finally, an organic diode was fabricated to determine charge carrier mobility of the complex using a steady-state method.