We report the development of techniques to diagnose plasmas produced by X-ray photoionization of thin foils placed near the Z-pinch on the Sandia Z Machine. The development of 100+ TW X-ray sources enables access to novel plasma regimes, such as the photoionization equilibrium. To diagnose these plasmas one must simultaneously characterize both the foil and the driving pinch. The desired photoionized plasma equilibrium is only reached transiently for a 2-ns window, placing stringent requirements on diagnostic synchronization. We have adapted existing Sandia diagnostics and fielded an additional gated 3-crystal Johann spectrometer with dual lines of sight to meet these requirements. We present sample data from experiments in which 1 cm, 180 eV tungsten pinches photoionized foils composed of 200{angstrom} Fe and 300{angstrom} NaF co-mixed and sandwiched between 1000{angstrom} layers of Lexan (CHO), and discuss the application of this work to benchmarking astrophysical models.