Devitrification of glass with a cation ratio corresponding to the composition {Bi2.1Sr2CaCu2Ox+0.4Sr1.7Ca1.3Al2O6} was studied. At temperatures below 600 °C, the phases crystallized in the order Bi-2201, Cu2O, CaO, (Sr,Ca)3Bi2O6, while Al ions concentrated in the remaining glass. Above 600 °C, Bi-2212 and (Sr,Ca)3Al2O6 formed simultaneously, so that at 750 °C, the two-phase composite Bi-2212-(Sr,Ca)3Al2O6 was obtained that contained grains of the aluminate phase 0.03-0.3 µm in size. The Al-rich phase surplus increased the stability of the glass and accelerated Bi-2212 phase formation, while development of superconductivity in Bi-2212 was slowed down. It was shown that composite glass-ceramics with bulk superconductivity could be obtained at temperatures above 850 °C.