Two isostructural tellurite phosphates Ni₂M^IITe^IV₂O₂(PO₄)₂(OH)₄ (M^II = Ni, Zn) have been synthe- sized via hydrothermal method. Both of them crystalize in monoclinic space group C2/m (No. 12). For Ni₂ZnTe^IV₂O₂(PO₄)₂(OH)₄, a = 19.3247(10), b = 5.9697(3), c = 4.7737(2) Å, b = 103.637(5)°, V = 535.18(5) ų, Z = 2, M_r = 727.94, S = 1.103, D_c = 4.517 g·cm⁻³, μ(MoKα) = 11.434 mm^–1 and F(000) = 672, the final R = 0.0369 and wR = 0.1086 for 639 observed reflections with I > 2s(I). The crystal structure of Ni₂M^IITe^IV₂O₂(PO₄)₂(OH)₄ (M^II = Ni, Zn) features a 3D framework composed of [Ni₂O₂(PO₄)₂]⁶⁻ layers interconnected by [MTe₂O₂(OH)₄]²⁺ single chains. Different magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1) completely occupies the Ni(2) position but not partially substitutes both Ni(1) and Ni(2) position atoms. Additionally, the acentric TeO₃(OH)₂ tetragonal pyramids are aligned in an antiparallel manner, resulting in the crystallization of centrosymmetric (C2/m) crystal structure instead of the non-centrosymmetric crystal structure. The investigation of the origin of centrosymmetric crystal structure with strong dipole moment units provides deeper understanding for future rational design for non-centrosymmetric crystal structure.