•In situ DRIFT spectroscopy was employed to monitor the dust surface.•XRF, XRD and ICP-MS analyses were used for the chemical characterization of dusts.•Particles Size and the Ca/Si ratio could determine water adsorption onto dust.•At ambient relative humidity, natural mineral samples are always covered with water. The adsorption of water molecules on natural mineral dusts was investigated employing in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The natural dust samples originated from North and West Africa, Saudi Arabia and Gobi desert regions. Furthermore, the hygroscopicity of commercially available Arizona Test Dusts (ATDs) and Icelandic volcanic ash were examined. N2 sorption measurements, X-ray fluorescence and diffraction (XRF and XRD), as well as Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analyses were performed to determine the physicochemical properties of the particles. The water adsorption experiments were conducted in an optical cell, at room temperature under the relative humidity (RH) range of 1.9–95%. Results were simulated using a modified three-parameter Brunauer-Emmett-Teller (BET) equation. Water monolayer (ML) was formed in the RH range of 15–25%, while additional water layers were formed at higher RH. Besides, the standard adsorption enthalpies of water onto natural mineral dust samples were determined. A thorough comparison of two commercially available ATD samples indicated that size distribution and/or porosity should play a key role in particle hygroscopicity. Regarding the natural mineral particles, Ca/Si ratios, and to a lesser extent Al/Si, Na/Si, Mg/Si ratios, were found to impact the minimum RH level required for water monolayer formation. These results suggest that the hygroscopic properties of investigated African dusts are quite similar over the whole investigated RH range. Furthermore, one of the major conclusions is that under most atmospheric relative humidity conditions, natural mineral samples are always covered with at least one layer of adsorbed water.