Extensive analyses of low-temperature powder x-ray diffraction data for spinel LiMn2O4 (Fd3¯m at room temperature) make it clear that two structural phase transitions occur: first around 285 K from cubic to orthorhombic, second around 65 K from orthorhombic to tetragonal. At temperatures under 285 K, superlattice peaks appear in the diffraction pattern that were successfully indexed by tripling the a and b axes of the spinel unit cell. At 250 K, the unit cell is face-centered orthorhombic, Fddd, F2dd, or Fd2d, with a=24.855(1), b=24.755(2), c=8.2014(3) Å, V=5046.1(4) Å3, Dx=4.284 g/cm3, Z=72. The unit cell at 30 K was confirmed to be body-centered tetragonal I41/amd or I41/a, with a=17.5176(3), c=8.1961(2) Å, V=2515.1(1) Å3, Dx=4.298 g/cm3, Z=36.