Migration of transition metal (TM) ions to tetrahedral sites plays a crucial role on structural transformation and electrochemical behaviors for Li-rich layered oxides. Here, incorporating small B3+ in the tetrahedral interstice is employed to block the migration channel of TM ions and stabilize the crystal structure. Benefiting from their good structural stability, Li-rich layered materials with B-doped Li1.198Ni0.129Co0.129Mn0.535B0.01O2 and Li1.196Ni0.127Co0.127Mn0.529B0.02O2, exhibit excellent cycling performance and voltage stability. After 51 cycles at 0.2 C, 1 mol.% boron incorporated sample can deliver 211 mAh g−1 with capacity retention of 89.9%, which is much higher than that of the undoped sample of 177 mAh g−1 with the retention of 79.2%. Moreover, the declined voltage per cycle decreases from 3.6885 mV to 2.7530 mV after 2 mol.% boron doping. XRD patterns after extended cycling verified the suppression of the structural transformation by the incorporation of boron.