Australia is a highly developed country with low population density. Capital cities are situated mainly around the coastline and are subjected to different meteorological conditions. This complex set of drivers is expected to result in varying trends in particulate matter (PM) mass concentrations in urban ambient air across the country. Thus, the aim of this study was to determine the long-term trends in PM10 and PM2.5 concentrations in capital cities, and to analyse the factors that influenced such trends. The spatial variability of PM concentrations within the capital cities was first established to identify representative stations. Then trends were determined using the Mann-Kendall trend test, Sen's slope, and the generalised additive model. The results show that, in general, the PM concentrations in Australian cities are relatively low (12.1–21.7 μg m−3 mean daily PM10 and 4.6–8.7 μg m−3 mean daily PM2.5) and within the WHO daily limit 95% of the time. Over the past two decades, very small declines of 8.0 × 10−5–1.1 × 10−3 μg m−3.yr−1 for PM10 and 7.7 × 10−5–2.6 × 10−3 μg m−3.yr−1 for PM2.5 were observed while some stations exhibited increase in concentration based on available data; more stations showed a significant monotonic decline for PM10 than PM2.5. This is attributed to the effectiveness of the implemented emission reduction policies particularly for vehicle exhaust and power generation, given the simultaneous increase in the demand for energy and the number of vehicles over the last two decades. Regarding climate, in the coastal cities of Sydney and Brisbane, high rainfall and strong winds aid in maintaining low PM concentrations despite the significant anthropogenic emissions, while higher PM levels in Darwin can be attributed to its tropical savannah climate, which makes it prone to bushfires and necessitates regular prescribed burnings. PM concentrations increase when exceptional events such as bushfires and dust storms are induced by the extreme climate variability. Further reduction of PM concentrations in Australian cities is unlikely, considering the expanding urbanisation and the changing climate.