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Sulfuric acid (SA)‐dimethylamine (DMA)‐H2O cluster formation has been proven to be responsible for a significant part of new particle formation (NPF) in a Chinese megacity. However, the possible involvement of common atmospheric acids in the subsequent growth of SA‐DMA clusters remains elusive. We simulated formation and growth of clusters using atmospheric relevant concentrations of SA, DMA, and trifluoroacetic acid (TFA), a commonly observed atmospheric perfluorocarboxylic acid, using Density Functional Theory combined with Atmospheric Cluster Dynamics Code. The presence of TFA leads to complex cluster formation routes and an enhancement of NPF rates by up to 2.3 ([TFA] = 5.0 × 106 molecules cm−3, [SA] = 1.0 × 106 molecules cm−3, and [DMA] = 1.5 × 109 molecules cm−3). The agreement of (SA)1·(DMA)1‐2·(TFA)1 concentrations between simulations and ambient measurements during NPF events validates model predictions and implies that perfluorocarboxylic acids could potentially boost atmospheric SA‐DMA NPF rates. Plain Language Summary: Atmospheric nucleation is the earliest step to form new aerosol particles, which includes a complex transformation from gaseous molecules to small clusters, then to critical clusters, and finally to freshly nucleated nanoparticles. Sulfuric acid and dimethylamine have been proved to explain atmospheric nucleation events in urban China. However, whether other atmospheric acidic species could participate in this nucleation process remains elusive. Herein, we report a sulfuric acid‐dimethylamine based nucleation mechanism with the participation of trifluoroacetic acid, a commonly observed strong acid in the atmosphere, using theoretical calculation methods. The model predictions are then validated by ambient measurements in urban Shanghai. Our results suggest that perfluorocarboxylic acids could potentially boost the formation of nanoparticles. Key Points: Theoretical simulations indicate complex atmospheric new particle formation mechanisms involving sulfuric acid, dimethylamine, and trifluoroacetic acidGood agreement of key cluster concentrations between simulations and ambient measurements during new particle formation events is obtainedTrifluoroacetic acid can participate in the growth of sulfuric acid‐dimethylamine clusters and enhance the nucleation rates [ABSTRACT FROM AUTHOR]