Three ancillary ligands based on imidazo-bipyridyl with phenyl (Ph), naphthyl (Np), and triphenylamine (TPA) substitution were synthesized and secondhand to formulate the consistent europium(III) ternary complexes using thenoyltrifluoroacetone as an anionic ligand. The complete investigation of spectroscopic, photophysical, and electrochemical properties was carried out. The attained results for all the ancillary ligands and their corresponding Eu complexes were compared with one another. All the Eu complexes reveal a broad excitation band ranging from the near-UV to blue region, along with high intense emission and apposite color purity. To further understand the ligand-to-metal energy transfer (ET) process, the geometry of the ligand was optimized and the energy level location (singlet and triplet) was calculated by using DFT and TD-DFT calculations. On the basis of the theoretical calculation, the ET mechanism was proposed. From PL emission spectra in the solid state, complete ET occurs from Ph, Np based ancillary ligands to the Eu3+ ion, which yields a pure red emission, whereas the TPA functionalized based Eu complex shows incomplete ET. Fortunately, white emission was observed in the TPA based Eu complex in the solid state. The white LED was fabricated by using a white emitting complex integrated with 395 nm emitted LED (InGaN) chips under 20 mA forward-bias current. The excitation source from LED was fully observed by the complex shown for 3Eu and showed yellowish emission in different concentrations (the similar observation also reflected in solid). However, in the case of 1Eu and 2Eu complexes, they showed close to white emission. The Commission International de I'Eclairage (CIE) chromaticity coordinates are close to the National Television Standard Committee standard value for white emission, and in addition, the complex 3Eu coated with the blue LED chip (460 nm) by PMMA (1:10) showed bright white emission with CIE x, y values of 0.30, 0.33, respectively.