Partial replacement of Bi by Pb and Sb produces materials of high-Tc pure phase, with antimony playing an important role in accelerating the formation of the phase with the higher superconductive transition in the Bi–Sr–Ca–Cu–O system. The influence of the antimony precursors on the superconducting phases mechanism formation was examined. Using a solid state reaction route, two nominal compositions Bi1.6Pb0.3Sb0.1Sr2Ca2Cu3Oy and Bi1.6Pb0.4Sb0.1Sr2Ca2Cu4Oy were investigated. The sources of antimony were Sb2O3, αSb2O4 and a prepared mixture Bi1.9Sb0.1Ox. The mechanism formation of the phases upon annealing was investigated using X-ray diffraction and simultaneous thermal analysis. Electrical properties of the obtained materials were evaluated. The presence of the antimony ions determined a higher reactivity of the system as well as the promotion of the superconducting high-Tc phase enhancement.