As an emerging contaminant, tungsten’s distribution and speciation in soils are far from understood. In this study, two soil profiles near a typical abandoned tungsten smelter in Hunan Province, China were collected and investigated, to ascertain the binding and association of tungsten with different soil components and subsequently to understand its mobility. The data showed that past tungsten smelting activities resulted in elevated concentrations of both tungsten and arsenic in the soil profiles, both of which ranged from dozens of to a few hundred mg/kg. Nano-scale secondary ion mass spectrometry (NanoSIMS) was employed to quantify the distribution and association of tungsten with various other elements. Combined with sequential extraction and mineralogical analysis, the data from NanoSIMS showed that aluminosilicates including kaolinite and illite were the most important mineral hosts for tungsten, whereas arsenic was predominantly bound to iron (oxyhydr)oxides. Additional data from ¹³C nuclear magnetic resonance and X-ray photoelectron spectroscopy revealed that soil organic matter retained tungsten in deep soils (>70 cm) by binding tungsten through carboxyls on aromatic rings. Compared to arsenic, tungsten migrated deeper in the soil profiles, suggesting its higher mobility and potential risk to groundwater quality.