The challenge of quantitatively forming self-assembled heterodimers without other equilibrium by-products is overcome through self-sorting favored by the introduction of designed shape-complementary moieties. Such a supramolecular strategy based on cucurbit[8]uril-directed dimerization is further applied to generate hetero-chromophore dimers quantitatively, leading to efficient energy transfer (>85 %) upon photoexcitation.