NH3, SO2, NOx and the inorganic ions of PM2.5 in winter 2009, 2014 and 2016 were examined to investigate the change in NH3 and aerosol chemistry in Beijing, China. NH3 concentrations showed an increase by 59% on average, in contrast to the decrease of SO2 by 63% from winter 2009 to 2016. The mean mass ratio of NH3/NHx was 0.83 ± 0.12 in 2016, which is higher than those obtained in 2009 and 2014, implying more NHx remaining as free NH3 in 2016 winter. Our findings suggest that vehicles exhaust emissions are an important NH3 source in urban central atmosphere of Beijing in winter. Despite the observed NOx presenting declining trends from 2014 to 2016, nitrate concentrations even exhibited a significant increasing trend, which may be largely attributable to high NH3 levels. An in-depth analysis of measured NH3 and aerosol species in a heavy pollution episode in December 2016, combined with the acidity predicted by ISORROPIA II model demonstrated abundant NH3 most of the time in air, where NH3 is not only a precursor for NH4+ but also effect the neutralization of SO42− and NO3− in PM2.5. With high RH and low photochemical activity, elevated NO3− concentration was attributed to an enhanced heterogeneous conversion of NOx to HNO3 to form NH4NO3 in pollution transport stage. The decrease in NOx from high level and the increase in NH3, with peaks of SO42− occurring were observed in pollution cumulative stage. The aqueous-phase oxidation of SO2 by NO2 to sulfate might play an important role with high pH values. Our results suggested that the simultaneous control of NH3 emissions in conjunction with SO2 and NOx emissions would be more effective in reducing particulate matter PM2.5 formation. Display omitted •NH3 and the chemistry components of PM2.5 change significantly from 2009 to 2016.•Vehicles exhaust is an important contributor to NH3 in central Beijing in winter.•Increasing nitrate trend may be largely attributable to high NH3 levels.