To better simulate the photosynthesis in nature and realize the full utilization of the harvested energy, an effective way is to explore the applications of the ALHSs for photocatalysis. Considering the non-planar conformation of triphenylamine (TPA) and the excellent photostability of carbazole (Cz), two blueemitting energy donors (named as K-1 and K-2) based on TPA and Cz units were synthesized. The introduction of o-methyl group increases the torsion angle between phenyl ring and carbazole unit, which is beneficial to enhance the aggregated state emission. Therefore, both K-1 and K-2 exhibit obvious AIE properties. The as-prepared macrocycle K-1 can encapsulate guest molecules in the cavity to form supramolecular assemblies avoiding the self-quenching of fluorescence. As a control, the reference molecule K-2 is designed as a noncyclic structure. Then, TPA-based fluorophore PBTB showing orange emission was selected as a relay energy receptor, and red fluorophore Z1 used as the terminal acceptor. First, an efficient one-step energytransfer process was readily established between K-1 and PBTB, with the optimal donor/acceptor (K-1/PBTB) ratio of 1000:40, resulting in the ΦET of up to 82.6%. Under same condition, the K-2/PBTB assemblies gave a ΦET of 77.9% (Scheme 1). Then, introduction of Z1 to the binary system, the calculated ΦET was 66.4% at the ratio of K-1/PBTB/Z1 = 1000:40:14, while the resultant K-2/PBTB/Z1 assemblies gave a ΦET of 60.4% under the same ratio. In addition, bright white light emission was also observed with a CIE coordinate of (0.33, 0.34) at the ratio of K-1/PBTB = 200:1 and the ratio of K-2/PBTB = 500:3, respectively. More importantly, it was found that the ALHS based on macrocycle K-1 exhibited higher photocatalytic activity for the cross-dehydrogenated coupling (CDC) reactions under white-light in water, with a yield of up to 87%. Furthermore, several organophosphorus compounds were synthesized under optimized photocatalytic conditions. Thus, the tunable feature of the supramolecular strategy makes the macrocyclic AIEgen K-1 a promising candidate for the construction of efficient ALHSs for photocatalysis.