A novel green process was developed for the recovery of N,N-dimethylformamide (DMF) from the acid-containing DMF solution by adding dimethylamine into the acid-containing DMF system during the “primary distillation-continuous reaction-secondary distillation” process, with N,N-dimethylacetamide (DMAC) produced as by-product. The laboratory research and the pilot-scale test were carried out. The results show: dimethylamine can break the interaction between DMF and acetic acid; the crude DMF with purity of 95% and no acid was produced during the primary distillation process, and the recovery of DMF was about 80%; the acid reacted with dimethylamine, producing DMF and DMAC, with a conversion of 96%, and the concentration of acid in the mixture was reduced to 1.4% after the reaction; the distillate with 47% DMF and the residue with 97.7% DMAC were obtained from the reaction mixture in the secondary distillation process.