The present article reports the synthesis of three Eu(III) complexes [Eu(BA)3(2-ap)] (1), [Eu(HBA)3(2-ap)] (2) and [Eu(ABA)3(2-ap)] (3) (BA=benzoic acid, HBA=2-hydroxy benzoic acid, ABA=2-amino benzoic acid and 2-ap=2-aminopyridine) carried out in ethanol solution. The complexes were further doped with CaF2 nanoparticles and a change in the photoluminescence properties was observed. The compositions and structural investigation of the complexes were determined by elemental analysis and Fourier transform infrared spectroscopy (FTIR) which suggest the coordination of ligands with the central Eu(III) ion. The optical properties of the complexes were studied by Ultraviolet Visible absorption spectroscopy (UV–Vis) and photoluminescence studies (PL). The relative PL intensity was enhanced in the Eu(III) complexes doped with CaF2 nanoparticles as compared to the pure Eu(III) complexes, however the increase in intensity varied in the order of ligands ABA>HBA>BA. The photoluminescence lifetime decay curves also revealed the longer lifetime (τ) and higher quantum efficiency (η) for europium complexes with ABA ligands suggesting the efficient energy transfer and better sensitizing ability of the ligand to europium ion. The morphology of the synthesized compounds were studied by Scanning Electron Microscopy (SEM) revealing spherical morphology with agglomeration of the nanoparticles.