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The vexatious difficulty in delineating percutaneous ablation margins of tumors in time represents a prominent obstacle toward better outcome of minimally invasive thermal ablation.To date, the ablative tumors images are often limited by inadequate spatial resolution and contrast in modern real-time imaging methods.Here we show a specifically exquisite "small-to-big" nanodroplet,which can help intra-operatively delineate the thermal ablation margins in real-time both in vitro and in vivo via a novel phase-transition strategy called microwave induced droplet vaporization (MWDV).Simultaneously,this nanodroplet,as a synergistic agent,can also significantly augment the efficiency of percutaneous ultrasound (US)-guided microwave ablation (MWA) both ex vivo and in vivo via a combinatorial strategy with US.This effect can make a contribution to solve other critical issues,such as incomplete ablation, in modern minimally invasive thermal ablation.Therefore, the successfully exquisite "small-to-big" nanodroplet provides an excellent platform for percutaneous US-guided MWA to enable more accurate ablation margin imaging and synergistic MWA efficiency of tumors.