Microexplosions are reported to occur frequently in droplet combustion of biodiesel mixed with alcohol, which are nominally miscible. We found, however, that they could be prevented if the standing time of fuel samples before burning was sufficiently long. To realize the microexplosion mechanisms, experiments based on suspending droplets and free-falling droplets were conducted. It was found that, before ignition, heterogeneous sites, which appeared similar to small drops, emerged from the droplet surface and subsequently merged into a bigger one, which then deposited at the bottom of the droplet. The diameter of this heterogeneous drop enlarged with increasing ambient humidity. At the same humidity, by using methanol, ethanol and isopropanol, respectively, the experiments showed that the merged heterogeneous drop of biodiesel/methanol was the largest and the smallest one was generated by that mixed with isopropanol. These heterogeneous sites were likely caused by the hygroscopic characteristics of alcohol fuels, which were supposed to mix well with biodiesel fuel and treated as a miscible blend in the first place. The miscibility, however, was destroyed by the absorbed water and phase separation occurred, leading to microexplosions when the droplet was burned. On the other hand, the interior heterogeneous drop vanished after sufficiently long time of standing prior to burning, and consequently no microexplosion was observed during the whole combustion process. For the mixture fuel of alcohol, methanol had higher propensity to absorb water and needed longer standing time for dissolution of the heterogeneous drop, as compared to ethanol and isopropanol, which had lower hygroscopicity. From the results, the heterogeneous sites inside the blended droplet were concluded unambiguously to be the primary cause of microexplosions during the combustion process, leading to the highest burning rate at equi-volume proportion of mixed fuels. In contrast, elimination of the heterogeneous sites in the burning droplets could prohibit microexplosions and yielded the highest burning rate at 25% fraction of alcohol. (C) 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.