In summary, novel supramolecular ALHSs based on AIE-active macrocycle K-1 was constructed, which successfully achieved one-step and two-step FRET processes. Thanks to the typical AIE property, undesirable fluorescence quenching is effectively avoided during the FRET process. By contrast with the non-cyclic AIEgen K-2, the ALHSs based on rigid macrocyclic molecule K-1 exhibited higher energy transfer efficiency, which was calculated to be 82.6% for the K-1/PBTB system and 66.4% for the K-1/PBTB/Z1 system, respectively. Bright white light emission can be successfully achieved at the ratio of K-1/PBTB = 200:1 and K-2/PBTB = 500:3 with CIE coordinates of (0.33, 0.34), respectively. More importantly, the ALHS based on macrocycle K-1 exhibited higher photocatalytic activity for the cross-dehydrogenated coupling (CDC) reaction under white-light in water, with yields of up to 87%. Thus, the flexibility of this novel supramolecular strategy makes macrocyclic AIEgen K-1 a promising candidate for the construction of efficient ALHSs for photocatalysis.