Environmental, safety, and availability constraints of mineral oils have led transformer manufacturers and researchers to turn to alternative liquid dielectrics to mineral oils. Thus, many works have focused on esters and more particularly on natural esters (NEs); commonly called vegetable oils; in recent decades. Besides their advantages (biodegradability, non-toxicity, recyclability, thermal stability, and safety) compared to mineral oils, natural esters have certain disadvantages including their high viscosity and their oxidation instability. Both of these properties can be improved by adding specific additives and nanoparticles. This paper is mainly focused on review of the breakdown voltage of natural ester-based nanofluids, one of the most significant parameters when selecting insulating fluids for high voltage devices and in particular for power transformers. Firstly, we take stock of the history of the introduction of fluids/oils in the field of electrical insulation and the return of vegetable oils in the transformer industry. Then, we present the main characteristics of vegetable oils and the different products based on vegetable oils currently on the market as well as those that are currently the subject of research and plants from which they come. The methods and techniques for the preparation/elaboration of these nanofluids and their stability are then exposed. Finally, we present the different results reported in the literature on the electrical breakdown of various types of natural esters when adding nanoparticles (NPs) issued from different materials (conducting, semiconducting, and insulating), under AC, DC and lightning impulse voltages, and discuss the involved mechanisms in the breakdown of nanofluids.