AbstractHexagonal boron nitride (h‐BN) has a layered lattice structure, high intrinsic thermal conductivity, and good chemical stability, and it has a promising applications in thermal management materials. However, poor interfacial compatibility and dispersion of BN flakes in the polymer matrix cause thermal contact resistance and gaps, directly impairing the performance of the composites and limiting their thermal conduction applications. Herein, the P‐BN@LM/PDMS thermally conductive composites with superior mechanical properties were fabricated by incorporating dopamine and liquid metal (LM) into BN flakes. The dopamine self‐polymerizes to form polydopamine (PDA) on the BN surface, denoted as P‐BN, which effectively improves interface compatibility and dispersion. The LM attaches to the functionalized P‐BN surface by mechanical grinding, acting as a bridge between adjacent BN flakes to enhance the integrity of the thermal conductive network within the composites. The coordination between P‐BN and LM increases interface strength, effectively improving mechanical performance. Hence, the P‐BN@LM/PDMS composites exhibit excellent thermal conductivity (4.0 W/mK) and an enhancement factor of 1373%, which is 2.22 times that of BN/PDMS composites with the same 30 wt% loading. Additionally, the composite shows superior tensile strength (2.11 MPa) and elongation at break (121%), representing 441% and 203% improvements compared with pure polydimethylsiloxane (PDMS). The P‐BN@LM/PDMS composites, with significant advantages in thermal conductivity and mechanical properties, are promising for future applications as flexible thermal interface materials in thermal management.Highlights The P‐BN@LM/PDMS composites exhibit excellent thermal conductivity (4.0 W/mK) and an enhancement factor of 1373%, making them promising for future applications as flexible thermal interface materials in thermal management. The P‐BN@LM/PDMS composites present a superior tensile strength (2.11 MPa) and elongation at break (121%). PDA formed by the self‐polymerization of dopamine on the BN surface effectively enhances interfacial compatibility and dispersion. LM attaches to the functionalized BN surface through mechanical grinding, acting as a bridge between adjacent BN flakes, thus enhancing the integrity of the thermal conductive network within the composites.