The one-step synthesis of 2-hydroxy-2-(trifluoromethyl)-malonates is described. The nucleophilic trifluoromethylation of commercially available 2-oxo-malonates was possible by use of the Ruppert-Prakash reagent (Me3SiCF3) in the presence of a catalytic amount of bases such as tetramethylammonium fluoride (TMAF) or LiOAc in THE or DMF at room temperature. The method can be applied to the synthesis of unsymmetrical 2-hydroxy-2-(trifluoromethyl)malonates with a sterically demanding ester group. Gram-scale synthesis of 2-hydroxy-2-(trifluoromethyl)malonates and their derivatization to a trifluoromethyl barbituric acid derivative were demonstrated.