AbstractSamples with the nominal composition Bi2Sr2Ca1–xLixCu2Oy(x= 0.2,0.4, and 0.6) and Bi2Sr2CaCu2−xL1xOz(x= 0.4, 0.6, and 1.0) were prepared by the solid state reaction method. The role of L1 at both Ca and Cu sites in the Bi‐2212 composition were studied. From the X‐ray diffraction data it was found that the L1‐doped at the Ca site increases thec‐axis and that doped at the Cu site decreases thec‐axis. From the D.C. four‐probe resistivity data it was found that Li‐doped at the Ca site reduces theTcand the L1‐doped at the Cu site givesTc(0) above the liquid nitrogen temperature. It was observed that the L1 doping reduces the melting point of Bi‐2212 composition. The presence of Lithium was confirmed by inductive the