Photoemission has been studied for nearly 100 years as both a means of investigating quantum physics, and as a practical technique for transducing optical/x‐ray photons into electrical currents. Numerous x‐ray detection schemes, such as streak cameras and x‐ray sensitive diodes, exploit this process because of its simplicity, adaptability, and speed. Recent emphases on diagnostics for low temperature, high density, and short‐lived, plasmas for inertial confinement fusion has stimulated interest in x‐ray photoemission in the sub‐kilovolt regime. In this paper, a review of x‐ray photoemission measurements in the 50 eV to 10 keV x‐ray region is given and the experimental techniques are reviewed. A semiempirical model of x‐ray photoemission is disussed and compared to experimental measurements. Finally, examples of absolutely calibrated instruments are shown.