A supramolecular assembly was constructed based on the tetraphenylethylene derivatives (TPEs) and nor - seco -cucurbit[10]uril ( ns -Q[10]). Upon introduction of the dye Rhodamine B (RB) into the TPEs@ ns -Q[10] assembly, an energy transfer process can occur from the TPEs@ ns -Q[10] assembly to RB. Moreover, after the addition of Nile Red (NiR), a two-step sequential energy transfer process from the TPEs@ ns -Q[10] assembly to RB and then to NiR can occur. Additionally, the dye Eosin Y (ESY) was introduced into the TPEs@ ns -Q[10] assembly and an energy transfer process can take place from the TPEs@ ns -Q[10] assembly to ESY. To utilize the harvested energy from the TPEs@ ns -Q[10]-RB-NiR and TPEs@ ns -Q[10]-ESY system, we applied the TPEs@ ns -Q[10] assembly-based light-harvesting systems (LHSs) as a catalyst for the advancement of the photocatalytic dehalogenation reaction in aqueous solution. When promoted with 0.5 mol % catalyst, the reaction yield reached 78 and 68%, demonstrating the promising potential of TPEs@ ns -Q[10] assembly-based LHSs in the promotion of the photocatalytic dehalogenation reaction.