Abstract Four years of observations of radon, meteorology and atmospheric pollution was used to demonstrate the efficacy of combined diurnal and synoptic timescale radon-based stability classification schemes in relating atmospheric mixing state to urban air quality in Zgierz, Central Poland. Nocturnal radon measurements were used to identify and remove periods of non-stationary synoptic behaviour (13–18% of each season) and classify the remaining data into five mixing states, including persistent temperature inversion (PTI) conditions, and non-PTI conditions with nocturnal conditions ranging from well mixed to stable. Mixing state classifications were performed completely independently of site meteorological measurements. World Health Organization guideline values for daily PM2.5/PM10 were exceeded only under strong PTI conditions (3–15% of non-summer months) or often under non-PTI stable nocturnal conditions (14–20% of all months), when minimum nocturnal mean wind speeds were also recorded. In non-summer months, diurnal amplitudes of NO (CO) increased by the factors of 2–12 (3–7) from well-mixed nocturnal conditions to PTI conditions, with peak concentrations occurring in the morning/evening commuting periods. Analysis of observations within radon-derived atmospheric mixing ‘class types’ was carried out to substantially clarify relationships between meteorological and air quality parameters (e.g. wind speed vs. PM2.5 concentration, and atmospheric mixing depth vs. PM10 concentration).