X-ray storage phosphors have several advantages over traditional films as well as digital X-ray detectors based on thin-film transistors (TFT). Commercially used storage phosphors do not have high resolution due to light scattering from powder grains. To solve this problem, we have developed storage phosphor plates based on modified fluorozirconate (ZBLAN) glasses. The newly developed imaging plates are “grainless” and, therefore, can significantly reduce light scattering and improve image resolution. To study the structure and image performance of the novel storage phosphor plates, we conducted X-ray diffraction (XRD) and X-ray imaging analyses at the Advanced Photon Source, Argonne National Laboratory. The XRD results show that BaCl2 crystallites are embedded in the glass matrix. These crystallites enlarge and are under residual stress after heat treatment. The X-ray imaging study shows that these storage phosphor plates have a much better resolution than a commercially used storage phosphor screen. The results also show that some of the glass ceramics are high-resolution scintillators. Our study demonstrates that these fluorozirconate-based glass ceramics are a promising candidate for high-resolution digital X-ray detectors for both medical and scientific research purposes.