The excitation and emission spectra of Eu3+ compounds (Eu(TTA)3phen andEuCl3.6H2O)are studied with the laser-excited ion(Eu3+) and high detection sensitivitytime-resolved luminescence technique. The experimental results demonstrate that thechanges of excitation spectra(especially for the 7F0→5D0 hypersensitive transition ) ofEu3+ are sensitive to the ligands. The ratios of the oscillator strength of hypersebSitivetransition (7F0→5D0) to that of magnetic dipole transition (7F1→5D0 ) from Eu3+ ionsin EuCl3·6H2O and Eu (TTA)3phen crystals are 0.031 and 0.067 transition, respectively. The splittings of 7F1→5D0 magnetic dipole transition, which depend on the strength and symmetry of the crystal field, are also measured. Under the resonant and nonresonant pulse excitations for 7F0→5D0 transition with a time duration of about 10 picoseconds, the immediately emission of 5D0→7F2,3,4 can be observed. This implies that the population time of 5D0 energy level is less than 10 picosecons under the laser-excited Eu3+. The experimental result also shows that there is a broad nonexponential decay fluorescence band with time constant from picoseconds to nanoseconds covering the spectral region of 5D0→7F2,3,4 transitions in Er (TTA)3 phen crystal.