The structure of the title dehydrated copper silicate, disodium dicopper undecaoxide tetrasilicate, Na2(Cu2O11Si4), was determined by single-crystal X-ray diffraction from a non-merohedral twin. It exhibits an effective three-dimensional microporous framework with the major channels, in which the Na+ cations are placed, running along the a-axis direction and smaller channels observed along the b-axis direction. The structure is unusual in that it contains a symmetry-constrained Si—O—Si angle of 180°. The Cu centre is coordinated to five O atoms, exhibiting a slightly distorted square-pyramidal coordination geometry. The Na cation is interacting with five neighbouring O atoms, exhibiting an uncharacteristic coordination environment.