In this study, multiple types of samples, including soils, plants, litter and soil invertebrates, were collected from a former arsenic (As) mine in China. The total As concentrations in the soils, earthworms, litter and the aboveground portions of grass from the contaminated area followed the decreasing order of 83–2224 mg/kg, 31–430 mg/kg, 1–62 mg/kg and 2–23 mg/kg, respectively. X-ray absorption near-edge structure (XANES) analysis revealed that the predominant form of As in the soils was arsenate (As(V)), while no arsenite (As(III)) was detected. In the grass and litter of the native plant community, inorganic As species (As(V) and As(III)) were the main species, while minor amounts of DMA, MMA, AsC, and an unknown As species were also detected in the extracts analyzed with high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The As speciation and As concentrations varied with the plant species, and very high As levels (197–584 mg/kg) and proportions of inorganic As (>99%) were found in two As-hyperaccumulating ferns, Pteris vittata and Pteris cretica. The major As species extracted from earthworms were inorganic, with proportions of 51–53% As(III) and 38–48% As(V). AsB was the only organic species present in the earthworm samples, although at low proportions (<8.99%). The internal bioconversion of other As species is hypothesized to contribute greatly to the formation and accumulation of AsB in earthworms, although the direct external absorption of organic As from soils might be another source. This study sheds light on the potential sources of complex organoarsenicals, such as AsB, in terrestrial organisms.