Heat dissipation has become a bottleneck restricting large-scale integration and flexible electronic technologies. This study reports a novel fabrication strategy to prepare flexible stachytarpheta jamaicensis flower-like hexagonal boron nitride nanoribbons (SJF-BNNBs) and their composite films with polyimide (PI). The effect of synthesis conditions on the morphology of SJF-BNNBs was investigated, and the growth mechanism was proposed. The in-plane and through plane thermal conductivities of the 4 wt% SJF-BNNBs/PI composite film reach 5.98 W m−1 K−1 and 0.79 W m−1 K−1, which are 3047 % and 316 % higher than those of the pure PI film, respectively. The in-plane and through plane thermal conduction enhancement efficiencies reach 761.8 % and 78.9 %, respectively. The tensile strength of the composite film is 61.7 % higher than that of pure PI, and maintains excellent electrical insulating and thermal stability properties. Infrared imaging tests verified the excellent heat dissipation performance of the composite film as a thermal interface material and a flexible copper clad laminate substrate, where the operating temperature of device could be reduced by 17.3 °C. To the best of our knowledge, SJF-BNNBs outperform the most efficient thermally conductive electrically insulating filler and are to break the overcome of polymer composites in heat dissipation applications.