This study examines the origin and distribution of clay minerals of the pedological horizons of Kori Ouallam watershed (south-western Niger). It is based on field sampling campaigns and a series of laboratory analyses. A total of 49 samples were analysed, 28 from surface horizons (0–10 cm depth) and 21 from pedological profiles (0–1 m depth). The samples were analysed by X-ray diffraction on bulk and clay (<2 μm) fractions, X-ray fluorescence spectrometry, laser granulometry, organic matter and calcium carbonate content, macroscopic observations (binocular loupe) and scanning electron microscopy equipped with an energy-dispersive spectrometry system. The pedological horizons are characterized by low organic matter contents (<1%) and no calcium carbonate. The particle-size distribution shows net textural differentiation, with a predominance of sandy loam to sandy clay loam textures in the upper horizons and clay loam to clay in the deep horizons. The main major oxides were SiO2 (46.3–89.0%), Al2O3 (5.0–24.2%) and Fe2O3 (1.0–27.9%). Kaolinite (64–98%) is the predominant clay mineral at all horizons, associated with low to moderate proportions of illite (1–34%) and traces of chlorite. Kaolinite is essentially inherited from the parent rock, whereas illite results from chemical alteration by bisialitization of the primary minerals initially rich in potassium feldspar contained in the parent rock. However, soil texture and organic matter vary independently with clay mineralogy. An extended study of all of the pedological facies that make up south-western Niger, combined with supplementary analyses, would further improve our understanding of clay mineralogy in the Sahelian zone.