Polymerization of N-substituted glycine N-thiocarboxyanhydrides (NNTAs) is a promising pathway to prepare functional polypeptoids benefiting from their tolerance to nucleophilic impurities. However, controlled NNTA polymerization is hard to achieve in amide polar solvents, including N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and N-methyl pyrrolidone (NMP), the only aprotic solvents for many biomacromolecules and polypeptoids. In the present work, we successfully achieve controlled NNTA polymerization in amide polar solvents by adding acetic acid as a promoter. The promotion is applied to the polymerization of sarcosine NTA, N-ethyl glycine NTA, and N-butyl glycine NTA. DMAc, DMF, and NMP are suitable solvents to prepare polypeptoids with designable molecular weights and low dispersities (1.06-1.21). The polysarcosines with high molecular weights are prepared up to 35.2 kg/mol. A kinetic investigation quantitatively reveals that the presence of acetic acid not only accelerates the polymerization, but also suppresses H2S-catalyzed decomposition of NNTAs by decreasing the concentration of H2S dissolved in polar solvents. Benzoic acid is also able to promote the polymerization, while trifluoroacetic acid, phosphoric acid, and phenol are not appropriate promoters. The moderate acidity of acids is essential. l-Methionine, l-tryptophan, and l-phenylalanine, which are dissolved in DMF, initiate the controlled polymerization of sarcosine-NTA in the presence of acetic acid and introduce functional end groups to polysarcosines quantitatively. In DMAc, hydrophilic vancomycin is grafted by poly(N-butyl glycine). The amphiphilic product dissolves in dichloromethane and stabilizes water-in-oil emulsion.