Ascorbic acid (AA), or vitamin C, is an important reactive biological molecule in vivo, and an abnormal level of AA is associated with many diseases. Therefore, the rapid, sensitive, and selective detection of AA levels is of significance in cases of medical assay and diagnosis. Compared with other nanoparticles, lanthanide coordination polymer nanoparticles (Ln-CPs) have been demonstrated as the excellent biomolecule sensing platforms due to their unique optical properties and intrinsic porosities. In this work, the cerium coordination polymer nanoparticles ATP-Ce-Tris were synthesized in a simple and quick way. The synthesized ATP-Ce-Tris nanoparticle shows the characteristic peak of Ce3+ located at 365 nm, which is corresponding to the 4f→5d transition of Ce3+. In the presence of Fe3+, the fluorescence of ATP-Ce-Tris quenched, and the following added ascorbic acid (AA) makes it restoring effectively. Based on this, we constructed a fluorescence probe with excellent sensitivity for AA sensing in a wide linear relationship from 0.05 to 500 μM. The detection limit was as low as 18 nM (signal-to-noise ratio of three), which is one or two orders of magnitude lower than those of reported sensors. The proposed sensing systems also exhibits excellent sensitivity for AA detection in human serum sample, exploiting a valuable platform for AA analysis in clinic diagnostic and drug screening.