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It was found in our previous work that hyperbranched polyester (HPE) can generate radicals and accelerate the chemical reactions of hydrocarbon fuels used as initiators. In this work, the evaporation and autoignition characteristics of JP-10 droplets with or without HPE were investigated using the high-speed backlight imaging technique in detail. The results indicate that the puffing and micro-explosion phenomena of HPE-blended JP-10 droplets can accelerate fuel evaporation and autoignition. When a 0.1% mass concentration of HPE was used, the droplet lifetime was reduced by 16.5% in evaporation at 850 K and 18.0% in autoignition at 900 K. A mechanism of HPE that promotes puffing and micro-explosions was proposed by analyzing droplet images of combustion and SEM images of combustion residues. Overall, this study provides a method for improving the evaporation and autoignition performance of JP-10.