A novel pyromellitic diimide-extended pillar[6]arene was synthesized in two steps with moderate yield for the first time. It showed a symmetrical stretched hexagon structure and could form 1:2 complexes with polycyclic aromatic hydrocarbons in solution. Interestingly, a linear supramolecular array between complex 1@G42 and pyrene through π···π stacking interactions was also observed in the solid state.