Efficient production of high‐quality, functionalized graphene is highly desirable for large‐scale applications of graphene. Herein, a route for producing high‐quality, polystyrene (PS)‐functionalized graphene is demonstrated via graphite exfoliation in chloroform with a heterobifunctional hyperbranched polyethylene, HBPE@Py@PS, as stabilizer. The HBPE@Py@PS, possessing a pyrene‐functionalized hyperbranched polyethylene backbone and multiple PS side chains, is synthesized by combining chain walking polymerization and atom transfer radical polymerization techniques. It is confirmed that the HBPE@Py@PS can effectively promote graphite exfoliation in chloroform under sonication to render stable dispersions of high‐quality graphene, with an exfoliation efficiency high as 15% and a monolayer proportion, 61%. Meanwhile, it can irreversibly adsorb on the exfoliated graphene surface based on the π–π stacking interactions, concurrently rendering PS‐functionalized graphene that is fluorescent and highly dispersible in chloroform, with a film conductivity reaching 1100 S m−1. The as‐produced graphene may find its applications as nanofiller for various PS‐based graphene nanocomposites.
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