The paper proposes novel molecular designs for rare-earth complexes involving the introduction of two different phosphine oxide structures into one rare-earth ion. These designs are effective for improving solubility and emission intensity. Additionally, the complexes are indispensable for realizing high performances in LEDs and security media. The thermodynamic properties of Eu(III) complexes are correlated with the solubility. Correlations between coordination structures and emission intensity were explained by NMR analysis. The luminous flux of red LED devices with Eu(III) complexes is very high (20 mA, 870 m lumen). A new white LED has its largest spectra intensity in the red region and a human look much more vividly under this light.