A discrete 2-nm-sized self-assembled organic capsule was formed from the union of six hexagram-shaped amphiphile molecules in aqueous methanol due to the hydrophobic effect, van der Waals forces, and CH-Pi interactions between the chemical components. A couple of hexa-substituted benzene molecules were encapsulated inside the capsule in both solution and the solid state, as was evidenced by H-1 NMR spectroscopy and single-crystal X-ray analysis.