The luminescent and lasing properties of Eu(III) complexes were enhanced by using an dissymmetric Eu(III) complex. The photophysical properties (the emission spectral shapes, the emission lifetimes, the emission quantum yields, and the stimulated emission cross section (SEC)) were found to be dependent on the geometrical structures of Eu(III) complexes. The geometrical structures of Eu(III) complexes were determined by X-ray single crystal analyses. The symmetrical group of Eu(hfa)(3)(BIPHEPO) (tris(hexafluoroacetylacetonato)europium(III) 1,1'-biphenyl-2,2'-diylbis(diphenylphosphine oxide)) was found to be C-1, which was more dissymmetric than Eu(hfa)(3)(TPPO)(2) (tris(hexafluoroacetylacetonato)europium(III) 1,2-phenylenebis(diphenylphosphine oxide): C-2 symmetry) and Eu(hfa)(3)(OPPO)(2) (tris(hexafluoroacetylacetonato)europium(III) 1,2-phenylenebis(diphenylphosphine oxide): C-2 symmetry). The analytical data were supported by Judd-Ofelt analysis. The most dissymmetrical Eu(III) complex, Eu(hfa)(3)(BIPHEPO), showed large electron transition probability and large SEC (4.64 x 10(-20) cm(2)). The SEC of Eu(hfa)(3)(BIPHEPO) was superior to even the values of Nd-glass laser for practical use (1.6-4.5 x 10(-20) cm(2)). The lasing properties of Eu(III) complexes in polymer thin film were measured by photopumping of a Nd:YAG laser (355 nm). The threshold energy of lasing oscillation was found to be 0.05 mJ. The increasing rate of the lasing intensity of Eu(hfa)(3)(BIPHEPO) as a function of the excitation energy was much larger than that of Eu(hfa)(3)(TPPO)(2) and Eu(hfa)(3)(OPPO)(2). The dissymmetrical structure of Eu(hfa)(3)(BIPHEPO) promoted the enhancement of the lasing property.