We present a combined theoretical and experimental investigation of photoionization along the Ne isoelectronic sequence and show that the near-threshold behavior of the cross section for Si 41 differs radically from the nearby ions in the sequence. We demonstrate that the general nature of the underlying physics implies that dramatic changes in near-threshold behavior may be expected for many other ions. PACS numbers: 32.80.Fb, 32.80.Hd, 52.25.Qt The response of positive ions to ionizing radiation, the fundamental process of photoionization, is a dominant process in the universe. However, it is largely unexplored experimentally due to the difficulty of producing and maintaining appropriate densities of multiply charged ions, along with the requirement for high-flux sources in the extreme UV and x-ray ranges [1,2]. Photoionization is particularly attractive for theoretical interpretation due to (i) selectivity, owing to dipole selection rules, (ii) the fact that the photon disappears, thereby simplifying the final state, and (iii) the weak coupling between the photon and target electrons, allowing focus on the many-body aspects of the electron-electron interactions of the target ion [3][4][5].From a fundamental point of view, positive ions provide a "laboratory" to investigate the dynamic interplay between many-body electron-electron correlations, electron-nucleus interactions, and relativistic effects by looking along an ionic sequence. With increasing ionization, as the electron-nucleus interactions dominate, the photoionization behavior will tend towards hydrogenic; however, this trend towards simplicity is not at all monotonic, and very significant changes in the cross section behavior may occur for particular ions. In this Letter, we report the first combined theoretical and experimental investigation of photoionization along the Ne isoelectronic sequence and show that the near-threshold behavior of the cross section for Si 41 differs radically from the nearby ions in the sequence. We demonstrate that the general nature of the underlying physics implies that dramatic changes in near-threshold behavior may be expected for many other ions.Photoionization of the Ne isoelectronic sequence, aside from its importance as the response of the simplest noble gas structure with multiple shells ͑1s 2 2s 2 2p 6 ͒ to ionizing radiation, is also of particular interest owing to the significant cosmic abundance of Ne, Na . Furthermore, the study of photoionization provides information on the inverse processes of radiative and dielectronic recombination which are of importance in modeling astrophysical [7] and laboratory [8] plasmas, particularly for low-energy electrons corresponding to the near-threshold region, which is the focus of this Letter.Following the pioneering work of Codling et al. [9], several extensive experimental investigations on neutral Ne have been carried out, aided by the relative simplicity of working with a gas and recent developments in storage ring sources [10]. For ions of the Ne sequence, previo...