Relying on the supramolecular self-assembly of twisted cucurbit[14]urils ( t Q[14]), anthracene derivatives (ADPy), Nile red (NiR), and rhodamine B (RB), highly efficient light-harvesting systems have been successfully designed in an aqueous medium. The addition of t Q[14] causes ADPy to aggregate through supramolecular self-assembly to form a supramolecular polymer (ADPy@ t Q[14]) with excellent aggregation-induced fluorescence and an interesting spherical external morphology, making it a remarkable energy donor. Consequently, efficient energy-transfer processes have occurred between ADPy@ t Q[14] assembly and NiR and RB, which both serve as effective energy acceptors while being loaded onto ADPy@ t Q[14]. In the case of NiR, the energy-transfer efficiency is up to 72.45%, and the antenna effect is near 55.4 at a donor/acceptor ratio of 100:1, making it close to the light-harvesting systems in nature. As a result, effective water-soluble artificial light-harvesting systems are showing enormous prospective as versatile platforms for simulating photosynthesis.