During supramolecular assembly, the positive photosensitizer should be pre-included in the cavity of SAC4A through charge-aided hydrogen-bonding interaction. Then, upon encountering hypoxic microenvironment, the as-obtained supramolecular complexes dissociated by reduction of azo group are essential to release the photosensitizer. Negative sulfonate groups decorated at the para-position of azobenzene are aimed to give a water-soluble calixarene and provide electrostatic interaction with positive AIEgen. The coneshaped SAC4A has a big 3D cavity that is large enough to encapsulate TPA-H. Therefore, our hypoxia-responsive hostguest assembly strategy is feasible theoretically. The detailed synthetic routes of TPA-H and SAC4A are presented in Scheme S1-S2. Their molecular structures were characterized by 1 H and C NMR and high-resolution mass spectrometry (HRMS) (Figure -S8, Supporting Information).