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We review recent work on the photoionization of atomic ions of astrophysical interest that has been carried out at the photon-ion merged-beams setup PIPE, a permanently installed end station at the XUV beamline P04 of the PETRA III synchrotron radiation source operated by DESY in Hamburg, Germany. Our results on single and multiple <i>L</i>-shell photoionization of Fe<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mo>+</mo></msup></semantics></math></inline-formula>, Fe<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></semantics></math></inline-formula>, and Fe<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></semantics></math></inline-formula> ions, and on single and multiple <i>K</i>-shell photoionization of C<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mo>−</mo></msup></semantics></math></inline-formula>, C<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mo>+</mo></msup></semantics></math></inline-formula>, C<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mrow><mn>4</mn><mo>+</mo></mrow></msup></semantics></math></inline-formula>, Ne<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mo>+</mo></msup></semantics></math></inline-formula>, and Si<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msup></semantics></math></inline-formula> ions are discussed in astrophysical contexts. Moreover, these experimental results bear witness of the fact that the implementation of the photon-ion merged-beams method at one of the world’s brightest synchrotron light sources has led to a breakthrough for the experimental study of atomic inner-shell photoionization processes with ions.