In the process of extraction of gold from refractory sulphide ores, arsenopyrite and pyrite represent two of the major hosts for gold in solid solution. In this study, the pressure oxidation of arsenopyrite and arsenopyrite-pyrite mixtures in a H2SO4–O2 system have been investigated, with the aim of using the oxygen consumption kinetics to probe the oxidation mechanisms. The effects of temperature (180–220 °C), acidity (pH 0.5–2.5), dissolved iron concentration (10 and 30 g/L) and molar ratios (0:1–3:1) of pyrite-to-arsenopyrite (Py/Aspy) were evaluated. Kinetic analysis of arsenopyrite dissolution at 180–220 °C via a shrinking core model indicated an activation energy (Ea) of 48.46 kJ/mol, suggesting a mixed interface reaction and diffusion control. The order of the reaction to acidity was 0.16 at 200 °C, suggesting that [H+] is likely not the rate-limiting factor under typical reaction conditions. The addition of Fe(II) ions to the feed enhanced arsenopyrite oxidation, due to the formation of Fe(III) as a surrogate oxidant to drive the reaction.The Ea for Py/Aspy of 1:1 exhibited two behaviours, calculated to be 77.32 kJ/mol below 200 °C and decreasing to 34.59 kJ/mol above 200 °C. The former was attributed to surface control due to the oxidation of elemental sulphur, followed by a switch to mixed control at elevated temperatures. As Py/Aspy was increased to 2:1 and 3:1, a single behaviour was observed, with Ea values of 56.01 kJ/mol and 43.35 kJ/mol respectively. These values imply a mixed control and begin to approximate literature values for pyrite oxidation. A time-to-a-given-fraction method was also used to examine changes in Ea with reaction extent. Arsenopyrite was found to be under mixed control for most of the reaction extent. At increasing pyrite fractions, oxidation was observed to be reaction-limited at the initial stage of reaction, potentially reflecting the kinetics of sulphur oxidation.