X-Shaped bolapolyphiles, comprising a linear polyaromatic core with glycerol groups at each end and two chemically different and incompatible chains, fixed to it at opposite sides, were synthesized and found to self-assemble into honeycomb-type liquid crystalline phases with square symmetry. The polyaromatic π-conjugated rods form the cell walls and the resulting prismatic cells of sub-5 nm size are alternatively filled with perfluorocarbon (RF) and the carbosilane chains (RSi). The resulting structures can be represented as either a two-colour snub-square tiling with triangular and square cells or as a chessboard tiling of squares.