The development of simple and efficient strategies for the preparation of various functional molecules from low cost and readily available starting substrates is one of significant goal in the field of synthetic chemistry. N,N-Dimethylformamide (DMF) is not only a common and excellent no-proton polar solvent, but also an important industrial raw material and a multipurpose synthetic reagent. The recent progress in the application of DMF as multifunctional reactant in carbonylation, formylation, ammoniation, carbamoylation as well as carbon source, hydrogen source and oxygen source The paper is reviewed.