X-ray diffraction and semiempirical methods have been used to investigate the structures of novel erbium(III) [Er(od)3(N,N-donor)] complexes, where od = 2,4-octanedionate and N,N-donor = 2,2′-bipyridine (bipy), bathophenanthroline (bath) or 5-nitro-1,10-phenanthroline (5NO2phen). Structural characteristics for these ternary complexes were also obtained by FTIR spectra. Subsequently, the visible and near-infrared luminescence properties of the compounds have been studied. Upon ligand excitation, the complexes show strong near-infrared luminescence at 1530 nm due to antenna effect. These erbium(III) complexes can potentially be applied to polymeric erbium-doped optical amplifiers, planar waveguides or infrared OLEDs.