Livestock grazing and topography have long been recognized as essential factors that control soil organic carbon (SOC) dynamics. However, the interplay effects of grazing and topography on SOC pool distribution and stability are not well understood, hindering the precise prediction of the organic carbon (OC) fate over the hillslope grassland. Here, we examine the relationship between grazing and topography on SOC pool distribution and stability in a Mongolian grassland. We determined a suite of OC metrics (e.g., particulate OC (POC), mineral-associated OC (MAOC), dissolved OC (DOC), and microbial biomass carbon (MBC) along a topographic gradient (e.g., upper slope, middle slope, and downslope) with grazing or not, and incubation was conducted to quantify OC stability. The results showed that POC and SOC content was 106–138% and 24–63% greater in the grazed than the ungrazed site at low topographic positions, respectively. Across the landscape, more variations in POC and SOC across the topographic gradient were observed at the grazed sites than at ungrazed sites. The MBC content of the downslope was greater in the grazing than in ungrazed sites. Furthermore, the humic-like substances in the grazing area were lower than those in the enclosed area and showed a significant and positive linear relationship with the aromaticity and humification of DOC. The aggregated boosted tree (ABT) analysis showed that the POC and MBC were the most important OC components to affect OC pool stability (accounting for 40.87%). The structural equation model (SEM) supported that the varies of POC regulated the downstream soil biochemical processes and changed SOC pool stability. Collectively, the results suggest the POC could be primarily responsible for the changes in SOC pools and stability in a hillslope grassland. These findings enhanced our understanding of the ecological mechanisms in SOC sequestration.