New synthetic methodology of the saturated and unsaturated Er(III)-chelated prototype complexes based on benzoate and pentafluorobenzoate ligands was developed through ligand-exchange reaction. The saturated 8-coordinated Er(III) complexes exhibit stronger near-IR emission than those of the unsaturated 6-coordinated Er(III) complexes, obtained from the direct photoexcitation of Er ions with 488 nm. Three $H_2O$ molecules coordinated in the unsaturated 6-coordinated complexes seriously quenched the near IR emission by the harmonic vibration relaxation decay of O-H bonds. Also, the stronger emission of the Er(III) complexes was obtained by the indirect photoexcitation of ligands than by the direct photoexcitation of the Er(III) ions, due to the energy transfer between the excited ligand and the erbium ion. Furthermore, the saturated Er(III)-chelated complex with C-F bonds shows much stronger near IR emission than that of the saturated Er(III)-chelated complex with C-H bonds. It is attributed to the influence of C-F bonds on near IR emission.