This paper presents for the first time the results of complex comparative tests on the lightning performance of a wide range of sustainable electrical insulating liquids made in GTL (Gas-to-Liquids) technology. Three different GTLs are compared with conventional mineral oils (inhibited and uninhibited) as well as biodegradable synthetic ester. Tests are aimed to determine Lightning Impulse Breakdown Voltage (LIBV) and Acceleration Voltage (Va) at standard lightning impulse voltage of both polarities. Those are performed at 25 mm gap distance of point-sphere electrode setup representing non-uniform electric field distribution. In addition, light emission is studied as well. Results show that for the conditions of experiment LIBV values tend to be similar for all tested dielectric liquids with a slight advantage of mineral oils at negative polarity and GTL-I oil at positive polarity. In turn, in terms of Va, it was found that at negative polarity the GTL oils are, in general, fully comparable with a high grade inhibited mineral oil. The Va of GTLs is in the range 260–275 kV versus 255–260 kV that characterizes mineral oils. When considering positive polarity the GTL-I is slightly inferior to other hydrocarbons with Va equal to 195 kV versus 230–255 kV characterizing other GTLs and mineral oils. For both polarities tested synthetic ester has much lower acceleration voltage in relation to hydrocarbon liquids including GTLs, which constitutes a huge disadvantage of the ester. Although the studies are limited to only one gap distance and non-uniform electric field distribution, it can be stated that the GTLs are worth to be examined as alternative to mineral oil when considering LIBV and Va as the analysed quantities. In addition, a special added value of the performed measurements should be mentioned that the measurements confirmed that Va parameter may be a good dielectric indicator of a dielectric liquid performance, especially when examining new product introduced to the market.