Here we report one-pot synthesis of tetraphenylethene-based tetracationic dicyclophane (1) and its self-assembly behaviors with aggregation-induced emission (AIE) and light-harvesting function. Confirmed by X-ray crystal structure and high resolution transmission electron microscopy, this tetracationic dicyclophane can self-assemble into a 3D supramolecular framework to form crystalline nanospheres (2) finally, which exhibits a strong emission (Phi(F) = 97.7%) via AIE effect in aqueous solution. Interestingly, AIE-active 2 as a single-molecule-based fluorescent supramolecular platform can encapsulate an organic dye (e.g., Nile red) to form light-harvesting nanospheres (3) further with a large red-shift (Delta lambda = similar to 70 nm), highly efficient energy-transfer ability (Phi(ET) = 77.5%), and high antenna effect (14.3).