Frequent desalter upsets in the refineries processing opportunity crude oils are often triggered by a rapid and uncontrollable buildup of the rag layer, a thick water-in-oil emulsion, at the oil-brine interface. This is caused by spontaneous emulsification of brine in oil. This study investigates a unique observation from a spinning drop (SD) tensiometer, revealing the low apparent interfacial tension and rigidity of SD caused by spontaneous emulsification. Fine droplets of brine generated through spontaneous emulsification decorate the SD surface and form a stable, low-energy bilayer. Simulated rag layers using the brines from upset incidences exhibit similar behavior, indicating that spontaneous emulsification is driven by chemical species in brine, which promote osmotic water transport. The rate of rag layer buildup correlates with the rate of spontaneous emulsification, with the temperature coefficient of interfacial tension reduction serving as a sensitive indicator. An imminent upset in the operation can be forecasted by measuring this temperature coefficient, enabling preventive measures.