Organic sulfur (S) mineralization is an important source of sulfate in soils, compared to atmospheric and weathering inputs. Previous studies on the effects of topography on the decomposition of organic matter have focused exclusively on mountainous regions with steep slopes, without considering low hilly regions with gentle slopes. It therefore remains unclear whether and how hilly regions create distinct environmental conditions that could affect organic S mineralization. We determined S sources, speciation and decomposition index in soil profiles and corresponding plant samples along a catena in a subtropical monsoon climate using a combination of S isotope ratios and S K-edge X-ray absorption near edge structure (XANES) spectroscopy. Sulfur in surface soils is mainly derived from decomposing litter. The decomposition of organic S is the primary process influencing the proportions of water-soluble and adsorbed SO42− in soil profiles. Pedogenic Fe and Al minerals contribute significantly to S stabilization in soils. The most oxidized S species are abundant in plants (10–56%) and may have the potential to stimulate biochemical mineralization through the hydrolysis of ester-S, thereby enhancing S-supplying capacity of soils. Water availability, influenced by small-scale topography, plays a key role in the S biological mineralization. The slower S decomposition rates at the lower elevation can be attributed to the high water content that inhibits microbial activities. Our results suggest that incorporating local-scale topography into the modeling frameworks may improve predictions of ecosystem S status and its responses to climate change.