The accumulation of arsenic (As) and antimony (Sb) by rice plants posed a great health risk to the residents around Xikuangshan, China, the world largest active Sb mining area. In this study, the pollution assessment of As and Sb in paired soil-rice samples was evaluated on the basis of field survey research. Moreover, the speciation and location of the these two metalloids in soil and rice samples were analyzed by the combination of wet chemistry, laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), synchrotron-based micro X-ray fluorescence mapping (μ-XRF) and micro X-ray absorption near-edge structure (μ-XANES) spectroscopy. The field survey indicated the paddy soil around studied areas was co-polluted by Sb (5.91-322.35 mg kg-1) and As (0.99-57.21 mg kg-1). Although the higher soil Sb concentration was observed, rice accumulated more As than Sb, indicating the higher bioavailability of As. In the rice grains, dimethylarsinic acid (DMA) was the predominant species and the percentage of inorganic As species was 19%–63%. According to µ-XRF mapping of the grain section, most of As were distributed and concentrated in the husk and bran part (mainly inorganic As) as well as in the embryo (As(III) and DMA). Sb distributed similarly to As in rice grain based on LA-ICP-MS. The results deepened our understanding about As and Sb pollution around Sb mining area.