Phase evolution, gas-phase particle size distributions and lead loss were studied during formation of (Bi,Pb)-Sr-Ca-Cu-O powders and their composites with silver by spray pyrolysis starting from nitrate solutions. The 10 wt% Ag/90 wt% Bi1.8Pb0.44Sr2Ca2.2Cu3Ox composite powders made at 700°C consisted of 20–60 nm grains of silver and mixed-oxide phases with a fine dispersion of Ag grains within the particles. At 700°C, the primary phases present in (Bi,Pb)-Sr-Ca-Cu-O powders were (Bi,Pb)2Sr2CuOx (2201), Ca2PbO4 (plumbate), (Bi,Pb)2Sr2CaCu2Ox(2212), and (Bi,Pb)3Sr2Ca2Cu1Ox(3221). For T≥800°C, the powders were considerably depleted in lead, and the plumbate and 3221 phases were absent. For T = 900°C, a large number of ultrafine particles (<30 nm) were formed, probably from the PbO vapor released from the reactor walls. Using spray pyrolysis, it is easy to control stoichiometry and limit the phase segregation at the nanometer-scale so that homogeneous and phase-pure materials can be obtained rapidly during subsequent processing.