Vipava valley in Slovenia is a representative hot-spot for complex mixtures of different aerosol types of both anthropogenic and natural origin. Aerosol loading distributions and optical properties were investigated using a two-wavelength polarization Raman LiDAR, which provided extinction coefficient, backscatter coefficient, depolarization ratio, backscatter Ångström exponent and LiDAR ratio profiles. Two different representative meteorological situations were investigated to explore the possibility of identifying aerosol types present in the valley. In the first case, we investigated the effect of strong downslope (Bora) wind on aerosol structures and characteristics. In addition to observing Kelvin–Helmholtz instability above the valley, at the height of the adjacent mountain ridge, we found new evidence for Bora-induced processes which inject soil dust aerosols into the free troposphere up to twice the height of the planetary boundary layer (PBL). In the second case, we investigated aerosol properties and distributions in stable weather conditions. From the observed stratified vertical aerosol structure and specific optical properties of different layers we identified predominant aerosol types in these layers.