This paper reports three new crystallographically characterized europium complexes with composition as follows: [Eu(fod)3(L1)] (1), [Eu(fod)3(L2)] (2) and [Eu(fod)3(L3)] (3) {L1 = benzimidazole (bzi), L2 = 4,7-diphenyl-1,10-phenanthroline (bath), L3 = 2-(2-pyridyl) benzimidazole (py-im) and fod = anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (Hfod)}. The single crystal (SC) XRD analysis shows that complex 1 is seven-coordinated while complexes 2 and 3 are eight-coordinated with the geometrical structures of a mono-capped octahedron and a trigonal dodecahedron, respectively. The NMR spectra of the complexes validate the SC-XRD results in solution. The complexes are stable in solution as no dissociation of any ligand was observed in the NMR spectra of the complexes. The photophysical properties of the complexes in solution, solid state, and PMMA thin films were studied. The hypersensitive transition 5D0 → 7F2 dominates the emission spectra in all phases, showing the highly asymmetric environment around the Eu(III) ion. The bath ligand is found to be the best sensitizer of the Eu ion and hence complex 2 shows the strongest luminescence properties with the highest absolute quantum yield among the three complexes. The CIE coordinate analysis shows that pure red-luminescence is emitted by the Eu complexes in the solid state since the coordinates found in this phase are closer to the standard NTSC 1987 values. The optical band gaps were determined for the complexes and the observed values suggest that the complexes can have possible applications in the field of semiconductor materials.