Passive solid-state detectors based on the visible radiophotoluminescence (RPL) of stable aggregate F2 and F3 + color centers in lithium fluoride (LiF) are successfully used for X-ray imaging and advanced diagnostics of intense X-rays sources. Among their advantages, these detectors offer a wide dynamic range and simplicity of use. They can be read non-destructively using a fluorescence microscope, enabling high spatial resolution over a large field of view. Optically transparent LiF films, of three different increasing thicknesses, were grown by thermal evaporation on glass and silicon substrates and subsequently irradiated with monochromatic 7 keV X-rays at several doses from 1.3 × 101 to 4.5 × 103 Gy at the SOLEIL synchrotron facility. For all the LiF films, the RPL response was found to depend linearly on the irradiation dose, with films grown on Si(100) substrates exhibiting up to a 50% higher response compared to those grown on glass. A minimum dose of 13 Gy was detected, despite the low thickness of the irradiated films. The limited thickness of the homogeneously colored LiF film allowed to obtain a spatial resolution of (0.44 ± 0.04) μm in edge-enhancement imaging experiments conducted by placing an Au mesh in front of the samples.