accessible with the conventional spectroscopic techniques such as absorption and emission spectroscopy, and in many laser-based applications such as isotope-selective photoionization processes, elemental ultra-trace analysis, etc. [8][9][10][11]. For the effective implementation of the processes mentioned above, identification of an efficient multi-step photoionization scheme is a prerequisite [1,11,12]. Precise information on photoexcitation and photoionization cross sections is necessary in the selection of an efficient multi-step photoionization scheme. It also helps in the distribution of the available tunable laser powers between various steps for efficient photoionization of atom.Several laser-based methods such as transition saturation [1,9,12], branching ratio and life time [12][13][14][15][16], Rabi oscillations [12], Autler-Towns [12,17] are reported in the literature by various research groups worldwide for the measurement of photoexcitation cross sections. With the exception of Mclaughlin et al. [18] who have measured the absolute photoionization cross section of Ti from the second excited level by observing the depletion in the fluorescence signal, the saturation method is the most suitable for the measurement of photoionization cross section [19][20][21][22]. The saturation in the photoionization signal represents the complete transfer of atomic population from the last excited level in the stepwise photoionization scheme. In this method, one has the advantage of measuring photoexcitation and photoionization cross sections using the same apparatus.The ionization potential of uranium is ~6.19 eV. Hence, a three-step photoionization of atomic uranium is the most appropriate using visible lasers whose photon energy is ~2 eV. In a three-color three-step photoionization process, i.e., λ 1 + λ 2 + λ 3 , where two-color photoionization, i.e., λ 1 + 2λ 2 , as shown in Fig. 1a, is not possible, photoexcitation and photoionization cross sections of the transitions used in a scheme are measured by observing saturation in Abstract Photoexcitation dynamics in a three-step photoionization of atomic uranium has been investigated using time-resolved two-color three-photon and delayed threecolor three-photon photoionization signals. Investigations are carried out in an atomic beam of uranium coupled to a high-resolution time-of-flight mass spectrometer using three tunable pulsed dye lasers. Dependence of both the signals on the second-step laser photon fluence is studied. Excited-level-to-excited-level photoexcitation cross section and photoionization cross section from the second excited level are simultaneously determined by analyzing the two-color three-photon and three-color three-photon photoionization signals using population rate equation model. Using this methodology, photoexcitation and photoionization cross sections at seven values of the second-step laser wavelength have been measured. From the measured values of the photoexcitation cross sections, we have obtained excited-level-to-excited-level transiti...