Abstract: High-entropy polymers (HEPs) represent a transformative approach to overcoming the intrinsic limitations of conjugated polymer photocatalysts through deliberate configurational disorder engineering. The designed high-entropy conjugated polymer Py-CNTh demonstrates exceptional photocatalytic performance, achieving hydrogen evolution and H₂O₂ production rates of 248.34 and 15.55 µmol h^-1, respectively—representing 8.8 and 43-fold enhancements over conventional counterparts (Py-Th). Comprehensive characterization reveals that entropy-driven structural disorder induces synergistic optoelectronic enhancements, as evidenced by a 33% reduction in exciton binding energy and a prolonged carrier lifetime of 919 ps, both of which contribute to significantly improved charge separation efficiency. The high-entropy architecture further strengthens interfacial processes through enhanced built-in electric fields and improved hydrophilicity. Systematic studies across an entropy increase establish a direct correlation between configurational disorder and photocatalytic performance, highlighting the critical role of entropy in optimizing charge transport and surface reactivity simultaneously. This work establishes high-entropy engineering as a general design principle for advanced polymeric photocatalysts, offering new opportunities for solar energy conversion applications.

Key words: High-entropy conjugated polymer, Photocatalytic hydrogen evolution, Photocatalyst, Donor-acceptor, Skeletal randomization strategy