Utilizing Europium(III), compounds having eight-coordination geometry of the type [Eu(hfpd)3L2] and [Eu(hfpd)3Lʹ] were synthesized [hfpd = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, L = tri-octyl-phosphine oxide (TOPO) and Lʹ = 1,10-phenanthroline (phen), Neocuproine (neoc) and bathocuproine (bathoc)] and characterized through elemental, FTIR, CV and Proton-NMR techniques. Photoluminescent studies and quantum yield helped to understand the role of coordination environment and ligands on the emission intensity. Luminescence decay curves served as the basis for calculating the excited-state lifetimes of the synthesized complexes. JO parameters (Ω2, Ω4) and asymmetry ratio were also evaluated to study the coordination environment around the central metal ion. Solid-state complexes exhibited an intense, monochromatic bright red emission, as characterized by its Commission International de l’Eclairage (CIE) color coordinates. Owing to red luminescence and semi-conducting properties, these Eu(III) complexes can be employed as red-emitting material for fabricating lighting devices.