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 L-shell photoionization of Fe+, Fe2+, and Fe3+ ions, and on single and multiple K-shell photoionization of C−, C+, C4+, Ne+, and Si2+ 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.