The effect of doping additional Bi on the magnetoresistance (MR) of La 2/3 Ca 1/3 B x Mn 1 -x O 3 was investigated. It is found that traditional colossal magnetoresistance (CMR) peak can only be observed in the x<0.05 samples and the peak value decreases with the increase of x, but the x≥0.05 samples show a magnetoresistance plateau above 200 K because of the presence of additional (La,Ca,Bi)-O layers. Moreover, this MR plateau is enhanced for the segregation of the La, Ca, and Bi elements.