Idealized large-eddy simulations were performed to investigate the impact of different mountain geometries on daytime pollution transport by thermally driven winds. The main objective was to determine interactions between plain-to-mountain and slope wind systems, and their influence on the pollution distribution over complex terrain. For this purpose, tracer analyses were conducted over a quasi-two-dimensional mountain range with embedded valleys and a flat foreland in cross-mountain direction. The valley depth was varied systematically. It was found that different flow regimes develop dependent on the valley floor height. In the case of elevated valley floors, the plain-to-mountain wind descends into the potentially warmer valley and replaces the opposing upslope wind. This superimposed plain-to-mountain wind increases the pollution transport towards the main ridge by additional 20% compared to the regime with a deep valley. Due to mountain and advective venting, the vertical exchange is 3.6 times higher over complex terrain than over a flat plain. However, the calculated vertical exchange is strongly sensitive to the definition of the atmospheric boundary layer height. In summary, the impact of the terrain geometry on the mechanisms of pollution transport confirms the necessity to account for topographic effects in future boundary layer parameterization schemes.