In order to better understanding clay mineral evolution coupled with geochemical changes during weathering of igneous rocks under temperate conditions, the picrite basalt-derived soil in Dali (South China) was investigated using X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM) methods. Our results show that smectite and mixed-layer clays occur throughout the weathered soil profile, while discrete kaolinite and illite phases are absent in the soil. From saprolite to topsoil, smectite decreases sharply, while mixed-layer kaolinite/smectite (K/S) and illite/smectite (I/S) clays increase markedly. Clay minerals in the saprolite consist of both dioctahedral and trioctahedral species, while those of the middle to upper profile display a uniform dioctahedral structure. I/S phases are characterized by interstratification of 12-Å smectite and 10-Å illite layers, and K/S phases by interstratification of 12-Å smectite and 7-Å kaolinite layers, with I/S/K clays containing all three layer types. Kaolinization of smectite occurs at the initial stage of weathering, earlier than that of smectite illitization. Desilication and K-fixation of smectite take place simultaneously during advanced weathering, resulting in formation of illitic and kaolinitic phases continuously throughout the developmental history of the soil. Notably high K concentrations in the weathering profile may be related to K-fixing in the interlayer of illite due to smectite illitization in response to more advanced weathering and pedogenic processes, while the increasing K content in the topsoil may be ascribed to fertilizer in land use and uptake of K by plants from deeper soil horizons. Fe2O3 and TiO2 accumulation in the topsoil is probably mediated by microorganisms.