The high altitude Puy de Dôme (PUY) research station, located at 1465 m a.s.l. in central France, hosts many instruments allowing continuous measurements and intensive campaigns to measure meteorological parameters, gas-phase species, aerosol and cloud properties. Aerosol chemical composition measurements provided by a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS) are used to evaluate the WRF-Chem model and more precisely its ability to simulate organic aerosol (OA) for a particular event in summer 2010. Using the Volatility Basis Set approach (VBS), dedicated to the formation of secondary organic aerosol (SOA), the WRF-Chem model strongly underestimates the high concentration levels of OA observed at the PUY station: 12.5 µg m–3 were observed and only 2.6 µg m–3 were simulated. By means of several measurements of gas-phase volatile organic compounds (VOCs), the robustness of both emissions and SOA formation processes in the WRF-Chem model was tested. The underestimation of the OA mass concentration appears to be mainly due to a misrepresentation of the oxidation rate of the organic condensable vapours (OCVs) and the SOA yields of both anthropogenic and biogenic VOCs in the VBS parameterization.