We have found a new phase of La0.05Sr0.95MnO3 with a 30-layer rhombohedral structure by using electron microscopy. The lattice constants were hexagonal axes of a = 0.5444 nm and c = 6.7582 nm. Both weak and strong intensities appeared in selected area diffraction (SAD) patterns. The strong intensities were caused by the periodicity of 15 (Sr,La)O-3 layers that had a new stacking sequence of (cchch)(3). However, the weak intensities indicated that the 15-layer structure has modulation along the c-direction that is twice as long as that of the structure indicated by the strong intensities. We concluded that the modulation of the 30-layer structure was produced by the introduction of two kinds of oxygen octahedra, Mn3+O6 and Mn4+O6.