From crystal structure, three types of translation and two types of orientation domain boundaries are expected in La 2/3 Ca 1/3 MnO 3 as a result of phase transition. However, the most easily observed domain boundaries in the bulk samples are ½ 1 2 0 translation boundaries were rarely observed. In this paper, this phenomenon is explained by considering the tilting modes of the oxygen octahedra in the structure. We found that there is no distortion to the nearby oxygen octahedra if the ½ 2 0 translation boundaries introduce a distortion in the oxygen octahedra, which requires breaking the tilting modes in the boundary areas and, therefore, they are high-energy boundary planes, which are rarely observed. The above-expected results are supported by our transmission electron microscopy data.