Polymer composites with good thermal conductivity are gaining more and more attention in the current electronics sector, due to their superior heat management capabilities. However, conventional thermally conductive polymer composites are usually subject to interruptions in heat transfer because of physical damage. The present study prepared mechanical property-enhanced thermally-conductive self-healing composites through compositing a self-healing polyurethane matrix with hydroxylated boron nitride (hyBNNSs). The self-healing polyurethane was obtained by incorporating ligands and cerium(III) triflate [Ce(SO3CF3)3] as the metal center into the polyurethane elastomer. An optimal sample (PUp2C) with high tensile strength (6.8 MPa) and stretchability (1053%), ideal toughness (49.2 MJ m-3), and remarkable healing efficiency (97% healing after 48 h at 35 °C) was obtained. An increase in the content of hyBNNSs from 10% to 30% led to a significant increase in the mechanical performance of hyBNNSs20%/PUp2C, which manifested as the increase in the elongation at break (from 1053% to 1302.5%) and stress (from 6.8 MPa to 16.4 MPa). The XRD results revealed that combining PU with hyBNNSs through coordination bonds could significantly promote the crystallization of PUp2C, which was beneficial to enhancing the mechanical properties of the composites. The through-plane (λ⊥) and the in-plane (λ∥) values of the BNNSs30%/PUp2C composite reached 0.41 and 1.42 W mK-1, respectively, which were 195.2% and 507.1% higher than those of the original PUp2C, respectively.