A Radial‐Linear π‐Conjugated Polymer by Integrating Poly(Para‐phenylene Vinylene) and Cycloparaphenylene for Enhanced Optoelectronic and Electrochemical Performance

Herein, we present a new class of hybrid conjugated polymer that integrates [8]cycloparaphenylene ([8]CPP) directly into poly(para‐phenylene vinylene) (PPV) frameworks, creating a π‐extended poly(cyclo(para‐phenylene vinylene)) ( [8]CPPV ). Comprehensive characterization confirmed its well‐defined alternating structure. Photophysical analyses revealed curvature‐driven electronic coupling between the radial CPP and linear PPV π‐systems, resulting in broadened absorption, red‐shifted emission, and high fluorescence quantum yield. Furthermore, [8]CPPV demonstrates excellent performance as a lithium‐ion battery anode, combining high initial capacity with stable cycling enabled by mixed pseudocapacitive and diffusion‐controlled Li + storage mechanisms. These results establish [8]CPPV as a versatile all‐carbon polymeric framework that bridges molecular nanohoops and extended π‐networks, offering a tunable platform for optoelectronic and energy storage applications.