Origin of life scenarios generally assume an onset of cell formation in terrestrial hot springs or in the deep oceans close to hot vents, where energy was available for non-enzymatic reactions. Membranes of the protocells had therefore to withstand extreme conditions different from what is found on the Earth surface today. We present here an exhaustive study of temperature stability up to 80 °C of vesicles formed by a mixture of short-chain fatty acids and alcohols, which are plausible candidates for membranes permitting the compartmentalization of protocells. We confirm that the presence of alcohol has a strong structuring and stabilizing impact on the lamellar structures. Moreover and most importantly, at a high temperature (> 60 °C), we observe a conformational transition in the vesicles, which results from vesicular fusion. Because all the most likely environments for the origin of life involve high temperatures, our results imply the need to take into account such a transition and its effect when studying the behavior of a protomembrane model.