Metal–organic frameworks (MOFs) have recently received a lot of interest for their use in adsorbing and eliminating hexavalent chromium from water. Obtaining low-cost, biocompatible, and environmentally friendly MOFs for research in this field is vital. One very stable three-dimensional UiO-66-Ce(IV) MOF, Ce-asp, was synthesized with a high yield using an amino acid ligand, DL-aspartic acid. As a result, the adsorption characteristics of the MOF against hexavalent chromium ions in aqueous solution were examined. The effects of time, solution pH, MOF dose, and beginning chromium(VI) content in aqueous solution were investigated on adsorption. More crucially, the adsorption mechanism of this MOF for chromium(VI) was proposed, setting the groundwork for its future use in chromium(VI) removal in real-world waters.