We report the synthesis of hyperbranched organic microwire (MW) networks comprising 1,4‐bis(pentafluorostyryl)benzene (10Ft) and 9,10‐bis(phenylethynyl)anthracene (BA) using a simple solution co‐assembly route. Pure 10Ft or BA assemblies cannot produce such complex MW networks; in contrast with a binary cocrystal of 10Ft and BA with a 2:1 molar ratio ((2:1)10Ft:BA), which is formed via intermolecular arene‐perfluoroarene (AP) interactions. A new generation of multiple MWs grow epitaxially on the previous generation of MWs to form MW arrays in which BA may also act as an intermediate product to facilitate the regeneration of (2:1)10Ft:BA. Highly aligned and well‐connected MW networks enable superior optical waveguiding ability. Moreover, a red‐emitting dopant, 5,12‐bis(phenylethynyl)naphthacene (BN) was incorporated into (2:1)10Ft:BA host MWs, giving light‐harvesting hierarchical MW networks via an energy‐transfer (ET) process. The realization of the hyperbranched MWs provides us with deep insight into the rational creation of complex branched arrays from functional organic cocrystals.

We report the synthesis of hyperbranched organic microwire (MW) networks comprising 1,4-bis(pentafluorostyryl)benzene (10Ft) and 9,10-bis(phenylethynyl)anthracene (BA) using as imple solution co-assembly route.P ure 10Ft or BA assemblies cannot produce such complex MW networks;in contrast with ab inary cocrystal of 10Ft and BA with a2 :1 molar ratio ((2:1)10Ft:BA), whichi sf ormed via intermolecular arene-perfluoroarene (AP) interactions.Anew generation of multiple MWs grow epitaxially on the previous generation of MWs to form MW arrays in which BA may also act as an intermediate product to facilitate the regeneration of (2:1)10Ft:BA. Highly aligned and well-connected MW networks enable superior optical waveguiding ability.M oreover, ar ed-emitting dopant, 5,12-bis(phenylethynyl)naphthacene (BN) was incorporated into (2:1)10Ft:BAh ost MWs,g iving light-harvesting hierarchical MW networks via an energytransfer (ET) process.T he realization of the hyperbranched MWs provides us with deep insight into the rational creation of complex branched arrays from functional organic cocrystals.