An organic–inorganic hybrid material based on paradodecatungstate building blocks and sodium–aminoacetic acid complex subunits,{Na10(H3N–CH2–COO)2[H2W12O42]}·28H2O (1), have been synthesized under mildly acidic conditions. This compound was characterized by single-crystal X-ray diffraction, elemental analysis, IR and UV–visible spectroscopies, and cyclic voltammetry. The compound crystallizes in the triclinic space group P-1 with a = 11.879(2) Å, b = 12.706(2) Å, c = 13.067(2) Å, α = 74.11(3)°, β = 79.71(3)°, γ = 65.95(3)°, V = 1727.2(5) Å3, and Z = 1. The crystal structure consists of infinite 2D layers constructed from [H2W12O42]10− clusters and sodium–aminoacetic acid complexes; adjacent layers are further joined by the complex units and sodium cations to yield a three-dimensional network.