The temperatures and pathways of crystallization for amorphous Bi–Sr–Ca–Cu–O are strongly dependent on oxygen partial pressure (Po2), the oxidation state of the glass, and the presence of Ag. Reducing the Po2 from 1 to 0 bar lowers the onset of melting 100 °C, but does not change the onset of crystallization. Decreasing Po2 does inhibit the formation of (CaSr)CuO3 (011). Although Ag appears to be immiscible in Bi–Sr–Ca–Cu–O, finely distributed Ag lowers the onset of melting by 20 to 35 °C, depending on Po2. In oxygen-deficient glass, two exotherms are observed upon heating. The first exotherm at 460 °C is independent of Po2, and Ag and corresponds with the formation of Bi2Sr2CuO6 (Bi-2201). The second exotherm occurs at 486 °C with Ag or 500 °C without Ag. The onset temperature of the second exotherm does not change with Po2, but the exotherm decreases in intensity with decreasing Po2. EXAFS indicates that in the as-quenched amorphous material, Cu is in a reduced state. Annealing the amorphous material in oxygen below the first exotherm (i.e., glass relaxation) increases the oxidation state of the Cu to that necessary for the formation of the Bi2Sr2CaCu2O8 (Bi-2212) without additional oxygen diffusion. This relaxation of the glass increases the crystallization temperature of the Bi-2201 to 500 °C. The crystallization sequence of Bi-2201 to Bi-2212 occurs at all Po2 ≥ 0.1 bar, but the composition of the secondary phases changes in the unrelaxed glass. Relaxing the glass eliminates liquid formation at low temperatures, allowing for rapid formation of the Bi-2212 phase with minimal formation of secondary phases for 0.1 ⋚ Po2 ⋚ 0.2 bar.