Allosteric regulation is extensively employed by nature to achieve functional control of protein or deoxyribonucleic acid through triggered conformational change at a remote site. We report that a similar strategy can be utilized in artificial self-assembly to control the self-assembled structure and its function. We show that on binding of metal ions to the headgroup of an amphiphile TTC4L, the conformational change may lead to change of the dipole orientation of the energy donor at the chain end. This on the one hand leads to a drastically different self-assembled structure; on the other hand, it enables light harvesting between the donor-acceptor. Because the Forster resonance fluorescence transfer efficiency is gated by metal ions, controlling the feeding of metal ions allows switching on and off of light harvesting. We expect that using allosteric self-assembly, we will be able to create abundant structures with distinct function from limited molecules, which show prominent potential for the postorganic modification of the structure and function of self-assembled materials.