Plumes from wildfires are transported over large distances from remote to populated areas and threaten sensitive ecosystems. Dense wildfire plumes are processed by atmospheric oxidants and complex multiphase chemistry, differing from processes at typical ambient concentrations. For studying dense biomass burning plume chemistry in the laboratory, we establish a Photochemical Large Aerosol Chamber (PHOTO-LAC) being the world's largest aerosol chamber with a volume of 1800 m3 and provide its figures of merit. While the photolysis rate of NO2 (jNO2) is comparable to that of other chambers, the PHOTO-LAC and its associated low surface-to-volume ratio lead to exceptionally low losses of particles to the walls. Photochemical ageing of toluene under high-NOx conditions induces substantial formation of secondary organic aerosols (SOAs) and brown carbon (BrC). Several individual nitrophenolic compounds could be detected by high resolution mass spectrometry, demonstrating similar photochemistry to other environmental chambers. Biomass burning aerosols are generated from pine wood and debris under flaming and smouldering combustion conditions and subsequently aged under photochemical and dark ageing conditions, thus resembling day- and night-time atmospheric chemistry. In the unprecedented long ageing with alternating photochemical and dark ageing conditions, the temporal evolution of particulate matter and its chemical composition is shown by ultra-high resolution mass spectrometry. Due to the spacious cavity, the PHOTO-LAC may be used for applications requiring large amounts of particulate matter, such as comprehensive chemical aerosol characterisation or cell exposures under submersed conditions.