Thermal conductivity enhancement in polymers is vital for advanced applications. This study introduces a novel method to align hexagonal boron nitride (hBN) nanosheets within polydimethylsiloxane (PDMS) matrices using a Halbach array to create a highly uniform magnetic field. This technique achieves significant improvements in thermal conductivity by effectively aligning hBN nanosheets. This research shows that hBN nanosheets, when aligned, can drastically enhance thermal conductivity in PDMS composites. Specifically, 10 wt.% vertically aligned hBN nanosheets in a rotating magnetic field achieve a thermal conductivity of 3.58 W mK−1, an impressive 1950% increase over pure PDMS. Additionally, the study explores the effects of orientation on dielectric properties, finding that the orientation of hBN nanosheets also improves electrical insulation and increases the dielectric constant while maintaining extremely low dielectric losses. For a vertically oriented sample, the dielectric constant reaches ≈14, and dielectric losses are as low as 0.0049 at 100 Hz, highlighting their potential for energy storage capacitors. This approach not only enhances thermal management but also maintains or improves electrical insulation, offering promising advances for polymer composites in various technological applications.