LAUSR

Excellent through‐plane thermally conductive composites are highly demanded for efficient heat dissipation. Giant sheets have large crystalline domain and significantly reduce interface phonon scattering, making them promising to build highly thermally conductive composites. However, realizing vertical orientation of giant sheets remains challenging due to their enormous mass and huge hydrodynamic drag force. Here, we achieve highly vertically ordered liquid crystals of giant graphite oxide (more than 100 µm in lateral dimension) by microwire shearing, which endows the composite with a recorded through‐plane thermal conductivity of 94 W m−1 K−1. Microscale shearing fields induced by vertical motion of microwires conquer huge hydrodynamic energy barrier and vertically reorient giant sheets. The resulting liquid crystals exhibit extremely retarded relaxation and impart large‐scale vertical array with bidirectional ordering degree as high as 0.82. The graphite array‐based composites demonstrate an ultrahigh thermal enhancement efficiency of over 35 times per unit volume. Furthermore, the composites improve cooling efficiency by 93% for thermal management tests compared to commercial thermal interface materials. This work offers a novel methodology to precisely manipulate the orientation of giant particles and promote large‐scale fabrication of vertical array with advanced functionalities.