The La Palma 2021 volcanic eruption was the first subaerial eruption in a 50-year period in the Canary Islands (Spain), emitting 1.8 Tg of sulphur dioxide (SO) into the troposphere over nearly 3 months (19 September-13 December 2021), exceeding the total anthropogenic SO emitted from the 27 European Union countries in 2019. We conducted a comprehensive evaluation of the impact of the 2021 volcanic eruption on air quality (SO, PM and PM concentrations) utilising a multidisciplinary approach, combining ground and satellite-based measurements with height-resolved aerosol and meteorological information. High concentrations of SO, PM and PM were observed in La Palma (hourly mean SO up to ~2600 μg m and also sporadically at ~140 km distance on the island of Tenerife (> 7700 μg m) in the free troposphere. PM and PM daily mean concentrations in La Palma peaked at ~380 and 60 μg m. Volcanic aerosols and desert dust both impacted the lower troposphere in a similar height range ( 0-6 km) during the eruption, providing a unique opportunity to study the combined effect of both natural phenomena. The impact of the 2021 volcanic eruption on SO and PM concentrations was strongly influenced by the magnitude of the volcanic emissions, the injection height, the vertical stratification of the atmosphere and its seasonal dynamics. Mean daily SO concentrations increased during the eruption, from 38 μg m (Phase I) to 92 μg m (Phase II), showing an opposite temporal trend to mean daily SO emissions, which decreased from 34 kt (Phase I) to 7 kt (Phase II). The results of this study are relevant for emergency preparedness in all international areas at risk of volcanic eruptions; a multidisciplinary approach is key to understand the processes by which volcanic eruptions affect air quality and to mitigate and minimise impacts on the population.