A detail process of sol–gel method was introduced to prepare V 2 O 5 –MoO 3 /TiO 2 catalyst powders containing different quantities of vanadium pentoxide and molybdenum trioxide in this study. Powder for the application in these SCR catalysts for mercury oxidation was tested in laboratory for the first time. The results indicated that titanium–vanadium–molybdenum catalysts are of higher mercury oxidation efficiency than titanium–vanadium catalysts. Especially the V 2 O 5 –MoO 3 /TiO 2 catalyst contained 5wt% vanadium pentoxide and 5wt% molybdenum trioxide (TV 5 M 5 ), even with only the present of 6% O 2 , it still performed a strong mercury oxidation ability. Elemental mercury oxidized by V 2 O 5 –MoO 3 /TiO 2 catalysts was found to follow the Mars–Maessen mechanism. Molybdenum trioxide could not directly oxidize Hg 0 , but molybdenum in high valence could assist to oxidize vanadium in low valence to increase the number of lattice oxygen for mercury oxidation according to the X-ray photoelectron spectroscopy results. In addition, HCl exhibited a promotional effect on mercury oxidation across TV 5 M 5 , the concentration of oxidized mercury escaped from the catalyst surface increased as the content of HCl introduced into the 6% O 2 /N 2 atmosphere increasing.