The monitoring of wildfire smoke is important to help mitigate impacts on people such as by sending early warnings to affected areas. Received signal levels (RSLs) from radio links have been used as an opportunistic way to accurately measure rainfall and humidity. Radio links provide integrated measurements along their paths and are an exceptional untapped resource to complement air quality stations in areas affected by smoke events, or in developing countries without air quality monitoring capability. This study analyzed radio link signal fluctuations during smoke events associated with the 2019–2020 Australian wildfires. Concurrently, the atmospheric boundary layer was characterized using atmospheric soundings and surface observations, as well as air quality proxies such as particulate matter concentrations less than 2.5 μm (10 μm), or PM2.5 (PM10). Observations showed that dry air containing large amounts of smoke within a surface layer above the ground acted as a lid, reducing dispersion, trapping and maintaining high ground-level concentrations of smoke. These conditions also created anomalous propagation conditions for radio links and operational weather radars. Power-law relations between signal fluctuations and PM10 and PM2.5 were derived based on the link data collected and the closest air quality station observations. While there was variability in retrieval performance across smoke events, the best performance determination coefficients exceeded 0.5, with an RMSE on the order of less than 50 μg m−3 for concentrations of more than 400 μg m−3. Mid-range link lengths (5–20 km) provided the best results.