A pseudo-D-5d symmetric decaaryl[60]fullerene molecule has a rigid bow-tie shape and bears an emissive [10]cyclophenacene chromophore in the middle. It forms a smectic liquid crystalline mesophase that persists over a wide temperature range (e.g., from 17 to 257 degrees C and shows yellow photoluminescence both in solution and in the solid state (inset in the POM image). Because of the alignment of the cyclophenacene chromophore in the lamellas, the bulk liquid crystals exhibit anisotropic photoluminescence.