Refractory gold and silver ores present significant challenges because precious metals are encapsulated within sulfide matrices, severely limiting extraction by conventional cyanidation. In this study, a pyritic concentrate from the Bacis Mine (Durango, Mexico) was characterized and subjected to two oxidative pretreatments—roasting and alkaline pressure oxidation—before cyanidation. X-ray diffraction confirmed pyrite to be the dominant phase, with quartz and minor carbonates contributing to the material’s refractory character. Roasting at 550 °C achieved gold and silver extraction of 80% and 70%, respectively, which improved to 89% Au and 74% Ag with the addition of hydrogen peroxide. In contrast, alkaline pressure oxidation at 150 °C and 1 MPa O₂ yielded the highest extraction of 92% for Au and 76% for Ag at 1 h. Thermodynamic analysis using the Fe–S Pourbaix diagram at 80 °C supported these experimental results, showing the destabilization of FeS₂ under oxidizing and moderately alkaline conditions. Overall, this study demonstrates that alkaline pressure oxidation is a technically efficient and environmentally favorable pretreatment for refractory gold ores.