Chlorination of triptycene tribenzoquinone 1H using sulfuryl chloride gives new perchlorinated derivative 1Cl, which exhibits a significantly enhanced electron-accepting property compared to 1H. Unlike 1H, due to complementary nested packing and π-stacking of the chlorinated benzoquinone blades in the crystal, 1Cl forms two-dimensional (2D) arrays, which stack up into a multi-layered structure. Considering the particular structure-forming ability, together with its strong electron-accepting property, 1Cl would provide an interesting building block for the design of 2D electronic organic materials.