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Anisotropic thermally conductive composites are very critical for precise thermal management of electronic devices. In this work, in order to prepare a composite with significant anisotropic thermal conductivity, polyamide 12/styrene–acrylic copolymer–boron nitride (PA12/SA–BN) composites with macro and micro double anisotropic structures were fabricated successfully using 3D printing and micro-shear methods. The morphologies and thermally conductive properties of composites were systematically characterized via SEM, XRD, and the laser flash method. Experimental results indicate that the through-plane thermal conductivity of the composite is 4.2 W/(m·K) with only 21.4 wt% BN, which is five times higher than that of the composite with randomly oriented BN. Simulation results show that the macro-anisotropic structure of the composite (caused by the selective distribution of BN) as well as the micro-anisotropic structure (caused by the orientation structure of BN) both play critical roles in spreading heat along the specified direction. Therefore, as-obtained composites with double anisotropic structures possess great potential for the application inefficient and controllable thermal management in various fields.