The spectra of odd-parity states of Eu atom are studied systematically with two-photon ionization detection technique. The two-photon ionization detection technique is utilized to obtain the spectra of odd-parity states with the two-step excitation: the wavelength of the first step laser is fixed, while that of the last-step laser is scanned around the region of 35 500-35 650 cm-1, 36 200-36 600 cm-1 and 46 650-46 950 cm-1, respectively. The characteristics of spectra in the energy region of 35 500-35 650 cm-1, 36 200-36 600 cm-1 and 46 650-46 950 cm-1 are investigated, demonstrating the special lifetime of highly excited states within those energy regions. In this paper, three different excitation pathways are used, not only the energy levels, line width and line shape are obtained, but also the q-reversal phenomenon is observed in the odd-parity states spectra. Besides, by analyzing the odd-parity states spectra of Eu atom, it is demonstrated that the possibility of 4f electrons are excited for the first time. © 2019, Science Press. All right reserved.