Centimeter size crystals of MnTeMoO6 have been grown by the top seeded solution growth method. The cleavage behavior and the single crystal structure of MnTeMoO6 crystal were analyzed. The total charge density of MnTeMoO6 was calculated. Cleavage behavior analysis indicates that a perfect cleavage behavior with {001} planes was found in MnTeMoO6 crystal. Single crystal X-ray diffraction analysis reveals that the MnTeMoO6 single crystal crystallizes in the noncentrosymmetric tetragonal space group P 4(4) over bar 42(1)m (No. 113) with cell parameters a=5.269(3) angstrom, c=9.014(11) angstrom and Z=2, and exhibits a novel neutral two-dimensional layered structure consisting of asymmetric MnO4 tetrahedra, TeO4 polyhedra and MoO4 tetrahedra. The total charge density analysis indicates that these layers are held together by van der Waals forces and the natural cleavage planes lie between the two proximate neutral layers. The results show that the layered structure connected by the weak van der Waals forces is the original of the cleavage in MnTeMoO6 crystal, and MnTeMoO6 crystal can be made into micro nonlinear optical device by stripping the cleavage layers. (C) 2015 Elsevier B.V. All rights reserved.