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Polymer/hexagonal boron nitride (h-BN) composites have attracted attention as heat dissipative materials for numerous electronic devices. Shusuke Yoshihara et al. reveal that a perpendicular relationship between the polymer and h-BN platelet orientations results in a dramatic enhancement of the composite thermal conductivity. The cover image shows crystalline lamellae align along the h-BN platelets, which are closely stacked one above the other. Polymer chains align perpendicularly to the platelets and behave as effective heat paths between the platelets, leading to the formation of a continuous thermal network. DOI: 10.1002/app.39768