AbstractMolecular carbons (MCs) are molecular cutouts of carbon materials. Doping with heteroatoms and constructing open‐shell structures are two powerful approaches to achieve unexpected and unique properties of MCs. Herein, we disclose a new strategy to design open‐shell boron‐doped MCs (BMCs), namely by pentagon‐fusion of an organoborane π‐system. We synthesized two diradicaloid BMC molecules that feature C24B and C38B π‐skeletons containing a pentagonal ring. A thorough investigation reveals that such pentagon‐fusion not only leads to their local antiaromaticity, but also incorporates an internal quinoidal substructure and thereby induces open‐shell singlet diradical states. Moreover, their fully fused structures enable efficient π conjugation, which is expanded over the whole frameworks. Consequently, some intriguing physical properties are achieved, such as narrow energy gaps, very broad light absorptions, and superior photothermal capability, along with excellent photostability. Notably, the solid of the C38B molecule exhibits absorption that covers the range of 300–1200 nm and an efficiency of 93.5 % for solar‐driven water evaporation, thus demonstrating the potential of diradicaloid BMCs as high‐performance organic photothermal materials.