An improvement in zero resistance temperature (T0c) of the 2223 phase in the Bi‐Sr‐Ca‐Cu‐O system by using a nominal composition Bi0.8Pb0.2SrCa2Cu2Oxhas been achieved. The bulk Bi0.8Pb0.2SrCaCu2Oxsamples synthesized from a matrix reaction method exhibited a superconducting transition withT0cof 110 K. Addition of one Ca‐atom per molecule of the above composition, that is, Bi0.8Pb0.2SrCa2Cu2Oxresulted in enhancedT0cof 122 K with onset temperature (Tonsetc) of 140 K. Interestingly,T0cof 122 K was also observed in the Pb‐free BiSrCa2Cu2Oxsamples, but it decreases to 115.5 K after 3–4 thermal cycles. However, no such decrease inT0cwas observed in the Pb‐doped samples, indicating the formation of stable 2223 phase. On the basis of x‐ray diffraction, energy dispersive spectra and scanning electron microscopy data, it is concluded that excess of Ca facilitate the nucleation of 2223 phase.