Two approaches were undertaken to characterize the arsenic (As) content of Chinese rice. First, a national market basket survey (n = 240) was conducted in provincial capitals, sourcing grain from China’s premier rice production areas. Second, to reflect rural diets, paddy rice (n = 195) directly from farmers fields were collected from three regions in Hunan, a key rice producing province located in southern China. Two of the sites were within mining and smeltery districts, and the third was devoid of large-scale metal processing industries. Arsenic levels were determined in all the samples while a subset (n = 33) were characterized for As species, using a new simple and rapid extraction method suitable for use with Hamilton PRP-X100 anion exchange columns and HPLC-ICP-MS. The vast majority (85%) of the market rice grains possessed total As levels < 150 ng g−1. The rice collected from mine-impacted regions, however, were found to be highly enriched in As, reaching concentrations of up to 624 ng g−1. Inorganic As (Asi) was the predominant species detected in all of the speciated grain, with Asi levels in some samples exceeding 300 ng g−1. The Asi concentration in polished and unpolished Chinese rice was successfully predicted from total As levels. The mean baseline concentrations for Asi in Chinese market rice based on this survey were estimated to be 96 ng g−1 while levels in mine-impacted areas were higher with ca. 50% of the rice in one region predicted to fail the national standard.