The oxidation roasting pretreatment process, which is a mature and dominant industrial practice for treating complex polymetallic gold deposits, has a low recovery of associated silver and exhibits an unclear reaction sequence. This study takes a silver-containing gold ore as the research object and investigates the effect of (i) sodium sulfite as an additive, (ii) main gold-bearing mineral pyrite, and (iii) gangue mineral quartz, on silver during the roasting process in roasting and leaching tests. Characterization techniques included scanning electron microscopy–energy dispersive spectroscopy analysis, and thermogravimetry–differential scanning calorimetry analysis. The results based on thermodynamic calculations and characterization show that the main reason for the low extraction of silver is that the calcined product (i.e., iron silicate) formed by the reaction between pyrite and quartz during the roasting process is mutually absorbed and wrapped with silver oxide. In addition, silver minerals decompose some iron sulfides and iron oxides under high-temperature conditions, promoting the reaction of iron and quartz to form iron silicate while strengthening the secondary encapsulation of silver by products of roasting, thus deteriorating the extraction of silver. The addition of sodium sulfite reduces the formation of iron silicate and increases the extraction of silver by directly promoting the conversion of pyrite to iron oxide. This study provides a theoretical basis for further improving the roasting and leaching of silver.