Microcrystalline (CH3NH3)MnTe2 was prepared by the reaction of LiMnTe2 and CH3NH3Cl in methanol at room temperature. The rearrangement of hexagonal [MnTeTe3/3] layers in LiMnTe2 to the tetragonal [MnTe4/2] layers found in (CH3NH3)MnTe2 is unprecedented and probably results from the dissolution of a small amount of LiMnTe2 with regrowth to accommodate bigger cations. Molecular mechanics calculations suggest that CH3NH3+ molecules are alternatively aligned (“up” and “down”) and tilted about 15° with respect to the c axis.