In this work, we describe a highly efficient and reabsorption-free X-ray-harvesting system using luminescent metal-organic framework (MOF)-fluorescence chromophore composite films. The ultrafast time-resolved experiments and density functional theory calculations demonstrate that a nearly 100% energy transfer from a luminescent MOF with a high atomic number to an organic chromophore with thermally activated delayed fluorescence (TADF) character can be achieved. Such an unprecedented efficiency of interfacial energy transfer and the direct harnessing of singlet and triplet excitons of the TADF chromophore led to remarkable enhancement of radioluminescence upon X-ray radiation. A low detection limit of 256 nGy/s of the fabricated X-ray imaging scintillator was achieved, about 60 times lower than the MOF and 7 times lower than the organic chromophore counterparts. More importantly, this detection limit is about 22 times lower than the standard dosage for a medical examination, making it an excellent candidate for X-ray radiography.