The effect of B concentration on the tunneling magnetoresistance (TMR) of (Co25Fe75)100−xBx/MgO/(Co25Fe75)100−xBx (x = 22 and 33) pseudo-spin-valve (P-SV) magnetic tunnel junctions (MTJs) was investigated. The TMR ratios for optimally annealed MTJs with x = 22 and 33 were 340% and 170%, respectively, at room temperature. High resolution transmission electron microscopy (HRTEM) observation showed a weaker (001) texture in the MgO barrier in the MTJ with x = 33. The bottom electrode was not fully crystallized even with a considerable amount of B in the (Co25Fe75)67B33, while good epitaxy was observed between (001) textured MgO and (Co25Fe75)78B22 electrodes.