The sensitive detection of UV light is critical in industrial production and for personal protection, and the aim of this research is to develop novel UV detection materials. The uranyl unit generally exhibits relatively high UV absorption efficiency and strong fluorescence intensity. Hence in this work, a uranyl coordination polymer compound [(TEA)₂(UO₂)₅(PhPC)₆] (TEA = tetraethylammonium ion, PhPC = (2-carboxyethyl)phenylphosphinic acid, denoted as UPhPC-1) was successfully synthesized via the hydrothermal method. The structural analysis of UPhPC-1 based on the single crystal XRD data elucidates that there are three crystallographically unique uranyl centers. Two uranyl units are in the pentagonal bipyramidal geometry, while the third one is in the tetragonal bipyramidal geometry. All three uranyl units are connected by the ligands to form infinite uranyl layers in the [bc] plane, which are packed via hydrogen bonding networks and π-π interactions to yield the overall layered structure. The stability test results of UPhPC-1 demonstrate that the compound exhibits good thermal and hydrolytic stability with high radiation resistance. Moreover, results of the UV irradiation experiments show that the intrinsic luminescence of UPhPC-1 is highly sensitive to 365 nm UV irradiation with a low detection limit and a fast response rate. A negative correlation between the emission intensity and the UV irradiation dosage was then established. The electron paramagnetic resonance data analysis strongly supports the production of radicals in UPhPC-1 under UV radiation, which leads to the partial quenching of the uranyl fluorescence. Furthermore, the radicals in the quenched sample can be readily eliminated by heating, resulting in the recovery of the photoluminescence intensity of UPhPC-1. The current results suggest suitable application potential of UPhPC-1 in the field of quantitative UV detection.