CeO2 was doped into Pd/Al2O3 using an impregnation method to suppress the interference of H2S and to improve the ability to capture elemental mercury (Hg-0) from syngas at high temperatures. As a result, the Hg-0 capture performance was generally enhanced by the incorporation of Ce as a result of the consumption of H2S. The individual presence of H-2 or CO resulted in the formation of Pd metal responsible for Hg-0 capture and active ceria in reduced form for H2S removal, thus promoting the Hg-0 removal. Meanwhile, H2S could react with CO to form COS, which competed with Hg-0 for active sites, hence inhibiting Hg-0 capture. The effect of HCl on Hg-0 capture over PCA sorbents was found to be slightly promotional, because a small amount of Hg-0 was oxidized to HgCl2. More importantly, the spent PCA sorbents could be easily reactivated, indicating that this material is a prospective candidate for Hg-0 control from syngas.