Recently, preoxidation is an effective pretreatment method of refractory gold ore, which has been widely used due to the high desulfurization, arsenic removal, low environmental pollution, and rapid reaction rate. In this paper, we describe the thermodynamic considerations of preoxidation of pyrite and arsenopyrite, the main minerals of the refractory gold ore, and the effect of the pressure oxidation, one of the preoxidation processes on the chlorination leaching. The thermodynamic results indicated that arsenopyrite under acidic conditions is easier to oxidize compared to pyrite and the oxidation decomposition of pyrite and arsenopyrite-type gold ore can be considered mainly for pyrite. The experiment has shown that the arsenic removal rate was higher than the desulfurization rate; it is confirmed that the thermodynamic conclusion of the oxidation of pyrite and arsenopyrite was correct. Comparing the XRD, SEM, and EDX analyses of gold concentrate and pressurized oxidation residue, it can be seen that the surface of pressurized oxidation residue is a fine porous structure and the dense and durable structure of sulfide ore is mainly destroyed.