Archaeological Dark Earth (ADE) pedogenesis and pre-Columbian history are fundamental for understanding the biodiversity and pedodiversity of the Neotropical rainforest in the Amazon region. This study aimed to evaluate the morphological, physical, chemical, and mineralogical properties as well as NaOH-extractable organic matter [OM(NaOH)] in ADE and Mulatto Earth (ME) overlying volcanic rocks along a toposequence (four soil profiles) in western Amazonia, Brazil. The soil profiles show anthropic A horizons over an argic horizon (Bt) in the ADE (Humic, Pretic Luvisols) and Bi in the ME (Clayic, Dystric Cambisols). The soil-forming processes in all of the profiles are associated with organic matter accumulation, such as humification and melanization, besides the formation of organometallic complexes. Calcium, Mg, P, and organic carbon contents were higher in ADE compared to ME. High-activity clays are derived from parent volcanic material, distinguishing the soils studied from Amazonian soils (Tertiary Plateau, Terra Firme) and most Amazonian anthropic soils. The anthropic horizons generally have a large contribution from OM(NaOH), predominantly humin and humic acids associated with Ca, Mg, and poorly crystalline Al hydroxides. The results suggest that the anthropic driving-forces caused greater differences in pedogenesis than the soil location in the landscape.