Organic perylene has been heralded as a promising candidate due to abundant structural diversity and tunability. However, its practical application is severely plagued by facile solubility, scarce redox-active sites, and andante kinetics behaviors. Herein, the perylene derivative (DPL), i.e., (1,6,7,12-tetrakis (4-tert-butylphenoxy) perylene-3,4,9,10-tetracarboxylic dianhydride) conjugates with polyoxime ester (PO) and is further nested with N, P grafted hollow matrix with anchored Cu single atoms (Cu-NPC). Such Cu-NPC@DPL@PO with helically twisted donor-π-acceptor (D-π-A) conjugate bridged by Cu atoms was evaluated for K