The superconductors with nominal composition of Bi2.0-xPbxSr1.9Ca2.2Cu3.3Oy were prepared by solid-state reaction method, XRD patterns were systematically studied for the samples. The results indicated that rich-Ca, Cu could accelerate the formation of (2223) phase, and broaden the sintering temperature range for a single phase. High-quality polycrystalline sample of 110K single phase was obtained. Annealing at lower temperature is beneficial to increase the volume ratio of 110K phase.