Kaolin samples from the Jari deposit (Amazon region) were studied using various techniques to characterize its structural and crystallochemical aspects, and to establish its origin and evolution. A profile 60 m thick was selected in a kaolin mine (Morro do Felipe) located at the banks of the Jari river. Despite the great thickness of the deposit and the variety of kaolin types, the mineralogical composition is rather homogeneous and is mainly kaolinite associated with gibbsite and small amounts of quartz, anatase, goethite and hematite. The field observations and the morphological analysis indicate the existence of sedimentary features throughout the whole profile except for the upper aluminous clayey layer (Belterra Clay). This is evidence that the Rio Jari kaolin deposit originated from sedimentary material, the Alter do Chão Formation. The presence of alternating clay and sandy layers is explained by sedimentation processes with great depositional energy variation. Thus, the accumulation of thick clay layers was related to a low-energy phase, and during the high-energy phases, the deposition process led to the accumulation of sandy materials, constituted essentially of quartz and showing strong textural and structural variation. Later on, periods of hydromorphy were responsible for iron removal and consequently for the bleaching of the sedimentary formation. The crystallinity data show an increase of the structural disorder toward the surface associated with an increase in the amount of structural Fe in the kaolinite. The Rio Jari kaolin deposits should be considered as having originated from kaolinitic clay sediments of the Alter do Chão formation (protore) that was submitted to intensive lateritic weathering processes.