Cold-air outbreaks (CAO) lead to intense air–sea interactions, the appropriate representation of which are fundamental for climate modelling and numerical weather forecasting. We analyze a CAO event with low-level wind speeds of approximately 25 m s−1 observed in the north-western Mediterranean Sea. The marine atmospheric boundary layer (MABL) was sampled with an aircraft equipped for turbulence measurements, revealing the organization of the MABL flow in coherent structures oriented along the mean wind direction, which was then simulated in two steps. First, a one-dimensional simulation enabled the determination of the forcing terms (particularly horizontal advection) required to adequately reproduce the vertical structure of the MABL flow. These terms were computed from a limited-area forecast model in operation during the entire field campaign. Then, a large-eddy simulation (LES) was performed during the well-established phase of the CAO event. The LES output is validated with respect to airborne data, not only with respect to the mean wind-speed and thermodynamic profiles, but also the turbulence statistics and coherent structures. The validated LES results enable description of the turbulent field as well as the coherent structures. The main discrepancy is a considerable underestimation of the simulated evaporation (computed with a parametrization of the turbulent surface fluxes), and hence of the moisture fluctuations throughout the boundary layer. Several possible explanations may explain this underestimation. The structure of the boundary layer is nonetheless well reproduced by the LES model, including the organized structures and their characteristic scales, such as the structure wavelength, orientation, and aspect ratio, which closely agree with observations. A conditional-sampling analysis enables determination of the contribution of the coherent structures to the vertical exchange. Although they occupy a limited fractional area, organized structures are the primary contributors to the turbulent exchange.