Cement plants (CPs) are one of the most important anthropogenic sources of mercury (Hg) emissions in China. Over 1000 cement production lines operate in China and use various raw materials; however, little data on Hg emissions is recorded on site. This study investigated a CP in Guizhou Province that uses multiple mining and industrial wastes as part of the circular economy policy. Among the various raw materials, carbide slag had the highest Hg content (2.6 mg/kg) and contributed half of the Hg input. High Hg concentration (27 mg/kg) in the kiln tail dust and a strong Hg enrichment factor (39) was found, which was determined as the ratio of total Hg accumulated within the clinker production process to the daily Hg input from raw materials and fuel. The clinker had negligible Hg (0.001 mg/kg), while the Hg in cement products (0.04 mg/kg) mostly came from additives and retarders. The estimated atmospheric emission factor of Hg from this CP was 161.5 mg Hg/t clinker, which was much higher than those of other CPs in Guizhou that employ low-Hg raw materials. A five-step sequential extraction experiment with kiln tail dust indicates that Hg mainly existed in fraction of F4 (73–96% of the total Hg, possibly as Hg₂Cl₂) and that some samples had high proportions of water-soluble Hg (up to 21% of the total), which may be easily released into surrounding water bodies and pose high environmental risks. Using low-Hg raw (or alternative raw) materials and conducting proper disposal of kiln tail dust will reduce the environmental risk of Hg from CPs.