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Ester liquids are environmentally friendly insulating oils, and they can be used as an alternative to mineral oil in transformers, even though in most countries spills of ester oils must be treated like spills of mineral oil. Furthermore, the breakdown characteristics of ester liquids are worse than those of mineral oils in heterogeneous electric fields. In this paper, we present a comprehensive experimental research on both positive and negative lightning impulse breakdown properties in point-plane geometries with gaps varying from 1 mm to 50 mm. The breakdown voltages and streamer velocities of five kinds of ester liquids, including natural ester, synthetic ester, and three kinds of single component esters have been measured. The results show that the double bonds have no effect on the breakdown voltage of ester liquids. The average streamer velocities of mono-esters are faster than that of other esters under positive polarity, and the breakdown voltages of all esters are close.