Although heavy metal pollution has developed into a major global environmental problem, most research has focused on specific elements, especially arsenic (As) and selenium (Se), and on the health risks to people in polluted areas or by occupation. This study investigated the urine of 480 participants from Guangzhou with a population of 18 million and targeted nine heavy metals: As, Se, chromium (Cr), manganese (Mn), nickel (Ni), cadmium (Cd), lead (Pb), antimony (Sb), and mercury (Hg). The heavy metals were widely detected, of which As, Se, Cd, and Pb all exceed 98%. Among the toxicants, As showed the highest concentration, followed by Se with 40.5 and 35.4μg/L, respectively. The heavy metal levels from suburban subjects were generally higher than those in urban subjects (except for Sb), and the Cd level of males was lower than that of females. Concentrations were related to age, body mass index, alcohol consumption, and smoking. According to the health risk assessment, most subjects experienced potential non-carcinogenic risk from As, Cd, Se, and Hg, which accounted for 38.2%, 8.83%, 8.31%, and 3.38%, respectively. The carcinogenic risk of As and Cd surpassed the risk level of 10-6, and 90.1% and 35.4% of the subjects, respectively, exceeded 10-4, an unacceptable risk level. More attention to the high carcinogenic risk from heavy metals and the high detected levels of As and Cd is required.