Litterfall is the main source of dry deposition of mercury (Hg) into the soil in forest ecosystems. The accumulation of Hg in soil and litter suggests the possibility of transfer to terrestrial invertebrates through environmental exposure or ingestion of plant tissues. We quantified total mercury (THg) concentrations in two soil layers (organic: 0–0.2 m; mineral: 0.8–1 m), litter, fresh leaves, and terrestrial invertebrates of the Araguaia River floodplain, aiming to evaluate the THg distribution among terrestrial compartments, bioaccumulation in invertebrates, and the factors influencing THg concentrations in soil and invertebrates. The mean THg concentrations were significantly different between the compartments evaluated, being higher in organic soil compared to mineral soil, and higher in litter compared to mineral soil and fresh leaves. Soil organic matter content was positively related to THg concentration in this compartment. The order Araneae showed significantly higher Hg concentrations among the most abundant invertebrate taxa. The higher Hg concentrations in Araneae were positively influenced by the concentrations determined in litter and individuals of the order Hymenoptera, confirming the process of biomagnification in the terrestrial trophic chain. In contrast, the THg concentrations in Coleoptera, Orthoptera and Hymenoptera were not significantly related to the concentrations determined in the soil, litter and fresh leaves. Our results showed the importance of organic matter for the immobilization of THg in the soil and indicated the process of biomagnification in the terrestrial food web, providing insights for future studies on the environmental distribution of Hg in floodplains.