Woodlot and natural woodland systems in the semi-arid regions in Tanzania are believed to have a high potential to sequester carbon (C) in their biomass and the soil which may qualify for C credits under the current voluntary C market schemes like, the REDD program. However, our understanding of the processes influencing storage and dynamics of C in soils under semi-arid agroforestry systems such as these woodlot systems is limited. This study evaluated C pools in soil and tree biomass in woodlot species of Albizia lebbeck, Leucaena leucocephala, Melia azedarach, and Gmelina arborea; and in farmland and ngitili systems. Synchrotron-based C K-edge x-ray absorption near-edge structure (XANES) spectroscopy was also used to study the influence of these land use systems on the soil organic matter (SOM) chemistry to understand the mechanisms of soil C changes. Soil samples were collected to 1 m depth and subsamples for each land use system to 0.4 m depth were fractionated into macroaggregates (2000-250 μm), microaggregates (250-53 μm), and silt and clay-sized aggregates (<53 μm) to provide information of C dynamics and stabilization in various land uses. SOC was analyzed in whole and soil aggregates and biomass C was estimated using developed biomass models from the literatures. Aboveground biomass carbon in the woodlots from the Kahama district ranged from 11.76 Mg C ha-1 to 24.40 Mg C ha-1. Based on the age of woodlots and the rate of carbon sequestration potential (CSP), Gmelina arborea had the highest rate of aboveground C sequestration (3.59 Mg C ha-1 year-1). The SOC stocks in whole soil for the land use systems from the two districts ranged from 43-67 Mg C ha-1. The degraded ngitili did not show a reduction in SOC stocks despite reducing aboveground biomass C stocks by 15.11 Mg C ha-1. SOC in the woodlots were found to be associated more with the micro and silt-and clay-sized aggregates than the macroaggregates, reflecting high stability of SOC in the woodlot systems. The XANES C K-edge spectra revealed the stabilization of recalcitrant aromatic C compounds in the silt and clay-sized aggregates. This study demonstrates the significant contributions of woodlots in biomass C accumulation as well as long-term SOC stabilization in soil fractions. Thus, these agroforestry practices hold promise to meet household energy needs while contributing to climate change mitigation and adaption.