N,N-Dimethylformamide derivatives 1a (Rf(6)-DMF) and 1b (Rf(8)-DMF) with a C6 or C8 fluorous ponytail, respectively, have been synthesized and examined for some physical properties. Rf(6)-DMF was tested as a solvent for Mizoroki-Heck arylation of butyl acrylate and Sonogashira coupling reaction of iodobenzene with phenylacetylene. Both reactions proceeded as smoothly as in DMF to give the products in high yield. Fluorous DMF derivative 1a can be recovered easily from the reaction mixture by a fluorous/organic biphasic workup and recycled.