The different amounts of manganese dioxide were doped to Ba4.5Sm9Ti18O54 (BST)ceramics. It was found that the doping sequence of Mn had serious influences on the microwave dielectric properties of the BST ceramics. When manganese dioxide was added before the mixtures were calcined, the dielectric properties of ceramics were poor and decreased with the increase of the Mn content. When the Mn content was between 2.0wt% and 3.0wt%, the BST ceramics had no microwave characteristic. But adding manganese dioxide in a range of 0.0 to 1.0wt% after the mixtures were calcined enhanced the microwave dielectric properties of the BST ceramics. When the Mn content changed from 0 to 1.0wt%, the microwave properties of the BST ceramics increased, but the microwave properties decreased while the Mn content was over 1.0wt%. The ceramics with 3.0wt% Mn content had also no microwave characteristic. The optimum microwave dielectric properties were as follows: εr=76, Q·f=7280,τf=-3.6ppm/k.