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Samples with the nominal composition, Bi1.84Pb0.34Sr1.91Ca2.03Cu3.06O10+δ high-Tc superconductors containing MgO as an additive were fabricated by a solid-state reaction method. Samples with MgO of 5~30 wt% each were sintered at 820~860 ℃ for 24 hours. The structural characteristics, critical temperature, grain size and image of mapping with respect to MgO contents were analyzed by XRD(X-Ray Diffraction), SEM(Scanning Electron Microscope) and EDS(Energy dispersive X-ray spectrometer) respectively. As MgO contents increased, intensity of MgO peaks and ratio of Bi-2212 phase in superconductors intensified and the proportion of the phase transition from Bi-2223 to Bi-2212 was increased.