A series of quenching experiments were conducted to understand the sequence of reactions that occur during the synthesis of doped Hg1223, (Hg, A)Ba2Ca2Cu3Oy, A = Re, Bi, and Pb (HgA1223). The formation and decomposition of the intermediate phases during the high-temperature reaction were followed as a function of temperature. HgA1223 phase forms over a wide range of temperatures, 750–950°C, 750–880°C, and 840–880°C for A = Re, Pb, and Bi, respectively. At T < 750°C, HgA1212 phase forms for A = Re and Pb. Based on the results of quenching experiments, heat treatment conditions were optimized for the synthesis of pure HgA1223 phase using commercial BaCaCuO precursor powders. A reduced-temperature annealing stage after the high-temperature reaction helps in grain growth and improves the microstructural characteristics of HgA1223 samples. Control of Hg pressure during the reaction is crucial for achieving phase purity, grain growth, and texture in the final products. A novel approach for the control of Hg pressure during the synthesis of HgA1223, which consists of using CaHgO2 as an external Hg source, is reported. HgA1223 samples synthesized using the new synthesis protocol exhibit improved microstructural and superconducting properties.