A pyrene-fused subphthalocyanine synthesized from a reaction of 2,7-di-tert-butyl-4,5,9,10-tetracyanopyrene and tetrafluorophthalonitrile exhibits red-shifted Q-band absorption and a unique linear arrangement in the solid state caused by a π-π stacking interaction. The concave conjugation of the SubPc moiety and the planar conjugation of the pyrene moiety enhanced its co-crystallization with C(60) molecules.