The substantial improvements in transmission voltage, which have been adopted to meet fast-growing energy demands, require more reliable power equipment and higher-quality insulating materials. The polytetrafluoroethylene (PTFE) nozzle, as the key part of a high-voltage circuit breaker, is often subjected to arc ablation and breakdown phenomena. Thus, it is very urgent to develop nozzles with better performance. In this study, PTFE/boron nitride (BN) composites were prepared. The relationships among the BN filler loading, thermal transition properties, spectral reflectance properties, arc ablation resistance, and AC dielectric breakdown performances, as well as their corresponding mechanisms, were studied. Experimental results show that the thermal conductivity and thermal diffusivity of PTFE/BN composites increased monotonously with BN loading, and that both parameters were improved by 41% and 44%, respectively, for 11 wt % composites compared with pure PTFE. Moreover, PTFE/BN composites had higher light reflectance in the wavelength range from 320 to 2500 nm. The PTFE/BN composites presented better arc ablation resistance performance with increased BN loading, which was improved by 88.5%. It is thought that the increased thermal conductivity, thermal diffusivity, the strong light reflectance, and surface sediment after arc ablation contribute to the improvement in arc ablation resistance performance. The AC breakdown strength of PTFE/BN composites was enhanced by 30.93%, attributed to the good heat dissipation properties introduced by the BN fillers. Thus, filling BN into the PTFE matrix would be helpful to solve the equipment issue that comes from the improvement in transmission voltage.