Parylene C is used in many applications due to its high properties but it remains a material with moderate performance as long as it is intended for use as an electret. Hence, the generally accepted idea, rightly so, in the scientific and industrial community not to necessarily select parylene (i.e., parylene C) for applications where the endurance of the electret is a strong criterion. Our study provided a new perspective on the performance of parylenes as electret. In this case, we will talk about fluorinated Parylenes of the VT‐4 type and especially AF‐4 variant. Their thermal stability is outstanding and a charge stability is almost total up to 100 °C. A 50% reduction in the charge is recorded at a temperature as high as of 220 °C (9 μm thick Parylene AF‐4), making it one of the most efficient polymer electrets to date. Negatively and positively charged Parylene AF‐4 electrets presented similar performance over long durations, which is out of ordinary for the commonly employed polymeric electrets. Finally, these fluorinated polymers are therefore particularly promising new candidates for applications in electret‐based converters for energy harvesting. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48790.