A novel aggregation-induced emission (AIE)-based artificial light-harvesting system (LHS) is successfully assembled via the host-guest interaction of bis-naphthylacrylonitrile derivative (BND), water-soluble pillar[5]arene (WP5), and sulforhodamine 101 (SR101). After host-guest assembly, the formed WP5⊃BND complexes spontaneously self-aggregated into WP5⊃BND nanoparticles (donors) and SR101 (acceptors) is introduced into WP5⊃BND to fabricate WP5⊃BND-SR101 LHS. Through the investigation of energy transfer between donors and acceptors, the artificial light-harvesting processes are certified in WP5⊃BND-SR101 LHS and the absolute fluorescence quantum yields (Φ