The Pleistocene Olorgesailie Formation in the southern Kenya Rift has yielded a remarkable assemblage of Acheulean artifacts and vertebrate fossils, including hominin specimen KNM-OG 45500. Members 1 and 7 both contain clay-rich deposits that have been pedogenically modified into paleosols (UM1p and UM7p, respectively). This study provides the first detailed mineralogical and geochemical analyses of the clays of this important Pleistocene basin. The smectitic clays, which show abundant evidence for pedogenesis, were apparently originally deposited under lacustrine conditions. They have an average structural formula of (Ca0.01Na0.32K0.26)(Si3.76Al0.24)(Al0.86Ti0.04Fe0.68Mg0.42)O10(OH)2. The high layer charge clays indicate diagenetic alteration of detrital clay derived from the volcanic drainage basin, probably involving alkaline waters of variable salinity. Despite overall lower salinity compared to other Plio–Pleistocene basins of the region (e.g. Olduvai Gorge), the basin still shows evidence for authigenic clay mineral precipitation. Clay chemistry and bulk geochemical indicators of pedogenesis imply that UM1p clays more closely reflect depositional paleo-waters, whereas UM7p clays have been more pedogenically altered due to subaerial exposure. UM1p smectites show some Mg enrichment near the western Lava Hump locality, consistent with discharge of Mg-bearing paleo-waters from a volcanic aquifer into a siliceous and alkaline (though not highly saline) paleo-lake. UM7p smectites were deposited in a more saline paleo-lake, but have lost substantial amounts of Mg due to post-depositional weathering. Locally abundant artifacts and vertebrate fossils found in these deposits accumulated at times following deposition of the lacustrine clay, probably concurrent with pedogenesis. The limnological conditions associated with initial clay deposition, therefore, preceded hominin occupation of the exposed surfaces.