Green tea has many health benefits and is the most consumed type in China. However, the heavy metals and contaminants in tea can also pose a great risk to human health. In this study, mercury (Hg) concentration in green tea collected from 11 provinces in China was examined. The leaching characteristics of Hg during brewing and the associated exposure to drinkers were also evaluated. Results indicated a low potential of Hg accumulation in green tea. The Hg content of green tea from Wanshan District, Guizhou Province—which has the largest Hg mine in China and is severely contaminated by Hg—could be limited by controlling the harvest time of tea leaves. The average Hg content of green tea from 43 tea production sites in China was only 6.3 ± 6.4 µg/kg dry weight. The brewing experiments of green tea showed that the leaching ratio of Hg was 22.61 ± 7.58% for 40 min of a single brew, and increased to 32.83 ± 12.37% after four rounds (3 min/ round) of brewing. The leaching of Hg from tea leaves was significantly affected by leaching time, temperature, and solid-liquid ratio but not by water hardness. The risk of Hg exposure from green tea intake was found to be very low, with an average hazard quotient (HQ) value of only 1.82 ± 1.85% for a single brew in 40 min and 2.64 ± 2.68% after four rounds of brewing. However, in some highly contaminated areas, with HQ values as high as 43.12 ± 2.41%, green tea intake may still pose a high risk of Hg exposure, and this risk should not be ignored.