Catalytic activity changes of perovskite catalysts were examined with their A-site substitution. For the preparation of catalysts, Mn was used for B-site component and La, Ce, Sr, Ba, Ca, Ag were used for A-site component of the perovskite catalysts(ABO3) The effect of calcination temperature on methane combustion and perovskite structure was also investigated. The surface area and adsorbed oxygen species were tested with BET apparatus and O2-TPD, respectively. Perovskite catalysts whose A-site was partially substituted needed higher calcination temperature than un-substituted one to form the perovskite structure. From O2-TPD experiment, it was found that methane combustion activity was directly related to the oxygen desorbing ability of the catalysts. The prepared catalyst(LM-7) was stable at 600℃ for 72 hours of reaction.