To explore the characteristics and sources of water-soluble inorganic ions in PM2.5 of Kunming, simultaneously on-line measurements of major water-soluble inorganic ions and gaseous pollutants were performed from April 15 to May 20, 2021 in Xishan district, Kunming city using a Gas-aerosol Collector and Ion Chromatograph (GAC-IC). The results showed that the average mass concentration of PM2.5 was 25.0±15.0 μg/m3, indicating that the atmosphere of Kunming was at a relatively clean level, and the average mass concentration of water-soluble ions was 8.32±4.83 μg/m3, which accounted for 32.1% of the PM2.5 concentration. The water-soluble components of PM2.5 and gaseous precursors showed obvious diurnal variation, with the increase of inorganic ion concentrations at night and the decrease of inorganic ion concentrations during the day after reaching their peak in the morning. The average SOR and NOR were 0.55 and 0.042, indicating that there was an obvious secondary transformation process of sulfate, but not of nitrate, which might be accompanied by the formation of nitrate and the decomposition of NH4NO3. The result of positive matrix factorization (PMF) indicated that there were five main contribution sources of water-soluble ions in PM2.5, which were fossil fuel combustion source and industry (36%), secondary sulfate (27%), biomass combustion (18%), secondary nitrate (16%) and sea salt (3%).