Bismuth calcium aluminate, Bi2Ca6Al12O27, has been prepared as a ceramic and a single crystal. Analysis of reciprocal space using both electron and X-ray diffraction show an R-centred hexagonal unit cell: a = b = 17.3892 (4), c = 6.986 (1) Å. Additional weak reflections are observed; they require the introduction of a modulation wavevector q = 0.0453 (2)c* for indexing. The modulated structure has been solved using the superspace formalism [superspace group X\overline{3}(00\gamma)0]. A framework of corner-sharing AlO4 tetrahedra forms corrugated sixfold rings and uncommon triple rings. The Ca2+ cations exhibit an eightfold coordination sphere; edge-sharing CaO8 polyhedra form intertwinned zigzagging rows along c creating a three-dimensional net. Bi atoms are located in large hexagonal tunnels parallel to c and form Bi2O3 pairs, which adopt a trigonal bipyramidal configuration. The 6s
2 lone-electron pairs (Lp) point along c, in the opposite direction to the three Bi—O strong bonds to form two BiO3Lp tetrahedra with a common base. Different orientations of the Bi2O3Lp2 pairs, rotated by 60° around c, are observed. Their stacking modes in each of the hexagonal tunnels are described. The sequence of the stacking varies along c in each of the tunnels.