The white beam (∼6–80 keV) available at the TopoTomo X-ray beamline of the ANKA synchrotron facility (KIT, Karlsruhe, Germany) was used to perform edge-enhancement imaging tests on lithium fluoride radiation detectors. The diffracted X-ray image of a microscopic boron fibre, consisting of tungsten wire wrapped by boron cladding, was projected onto lithium fluoride thin films placed at several distances, from contact to 1m. X-ray photons cause the local formation of primary and aggregate colour centres in lithium fluoride; these latter, once illuminated under blue light, luminesce forming visible-light patterns—acquired by a confocal laser scanning microscope—that reproduce the intensity of the X-ray diffracted images. The tests demonstrated the excellent performances of lithium fluoride films as radiation detectors at the investigated photon energies. The experimental results are here discussed and compared with those calculated with a model that takes into account all the processes that concern image formation, storing and readout