In this paper, we report a thermal conductive polymer composite that consists of silicone rubber (SR) and branched Al2O3 (B-Al2O3). Owing to the unique two-dimensional branched structure, B-Al2O3 particles form a continuous three-dimensional network structure by overlapping each other in the matrix, serving as a continuous heat conductive pathway. As a result, the polymer composite with a 70 wt% filler achieves a maximum thermal conductivity of 1.242 Wm−1 K−1, which is equivalent to a significant enhancement of 521% compared to that of a pure matrix. In addition, the composite maintains a high volume resistivity of 7.94 × 1014 Ω·cm with the loading of 70 wt%, indicating that it meets the requirements in the field of electrical insulation. Moreover, B-Al2O3 fillers are well dispersed (no large agglomerates) and form a strong interfacial adhesion with the matrix. Therefore, the thermal decomposition temperature, residual mass, tensile strength, modulus and modulus of toughness of composites are significantly improved simultaneously. This strategy provides new insights for the design of high-performance polymer composites with potential application in advanced thermal management in modern electronics.