Amazonian Dark Earths (ADE) are a particular type of soils developed between 500 and 8500 years B.P. through intense anthropogenic activities such as biomass-burning and charring, leaving high contents of black carbon (BC). The biogeochemistry of C and N in pyrogenic organic matter rich soils has been examined thoroughly, but no detailed information has been published on S speciation in BC- rich soils. Hence, the information about the amount, speciation and turnover dynamics of S in pyrogenic C-rich soils has been inferred from data generated from coal or crude oil products. This study investigates soil S fractions present in ADE soils at several chronological ages (up to 8500 years BP) compared to adjacent non-ADE soils (Oxisols). Total S in the soil samples was determined by NaOBr oxidation. Solid-state characterization of S oxidation states and S functionalities from the humic substances of ADE and adjacent soils samples were conducted by X-ray absorption near edge structure (XANES) spectroscopy at beam line X-19A (National Synchrotron Light Source, Brookhaven National Laboratory). The ADEs presented 1.6 to 3.4 times more total S than the adjacent soils. Most of the S was found in soil samples collected from the surface layers compared to the lower depths horizons in both the ADE and the surrounding adjacent soils.  Total S content decreased exponentially following the age of the ADE. The molecular-level information generated by XANES revealed that structural composition of soil organic S in both ADE and adjacent soils was remarkably similar. A decrease in ester-S accompanied by an increase in C-bonded S was observed with increasing age of ADE from 500-8500 years BP. Such detailed structural information can be used to further our understanding of factors regulating the biogeochemistry of S in ADE soils, thus reinforcing the role of organic S forms in the global S cycling.