We have investigated the details of phase separation in the electron-doped manganites Sm1-xCaxMnO3 (0.8≤x≤0.92) by using temperature dependent x-ray diffraction. The lattice of the low-temperature orthorhombic phase is distorted to various extents according to the strength of the coexisting monoclinic phase. Meanwhile, the room-temperature lattice becomes more distorted due to the increasing Jahn–Teller active Mn3+ ions by Sm3+ doping. On the other hand, the substitution of Ca2+ with Sm3+ introduces the Mn3+–Mn4+ pairs, which favor the double exchange ferromagnetism. As a result of the competition between the lattice distortion and electron doping level, the modified phase diagram have been presented, including the high-temperature Griffiths phase and the ground state with competing multiphases.