Melilite-type gallium oxides are potential intermediate temperature electrolytes for solid oxide fuel cells. Single crystals of [CaNd](2)[Ga](2)[Ga2O7](2) grown using an optical floating zone furnace have been investigated using transmission electron microscopy and powder and single-crystal X-ray diffraction. The anion array topologically conforms to a [(3.5.4.5)(2), 3.5.3.5] network that contains distorted pentagonal tunnels. The distortion is necessary to achieve space filling and accommodate structural misfit between the layers. Satisfactory bond lengths and angles are obtained through two-dimensional modulation in the tetragonal based plane, leading to five-dimensional symmetry in the superspace group P (4) over bar2(1)m(alpha,alpha,0)00s((a) over bar ,a,0)000, alpha = 0.2319(2), with modulation vectors q(1) = alpha(a* + b*) and q(2) = alpha(-a* + b*). Both displacive and occupational modulations are found. Through this mechanism, melilites are primed to accommodate mobile oxygen interstitials, suggesting a rational approach to crystallochemical tailoring that will enhance ionic diffusion and optimize electrolyte performance.