This paper presents an experimental study of the vapour space flammability of Fuel Ethanol (a high-ethanol fuel for Flexible Fuel Vehicles, commonly known as “E85”) and gasoline containing up to 10% ethanol (commonly known as “E10”). The seasonal minimum vapour pressure limits in specifications for automotive spark ignition fuels are intended, in part, to minimize the formation of flammable mixtures in the headspace of vehicle fuel tanks. This is particularly important at subzero temperatures, where the headspace mixture may not be rich enough to prevent combustion in the presence of an ignition source such as a faulty electrical fuel pump. In the current study, the upper temperature limits of flammability were measured for field samples of “E85” and “E10”, and a series of laboratory-prepared blends of denatured ethanol, Before Oxygenate Blending (BOB) gasoline, and n-butane. The paper compares the measured flammability limits with the ambient temperatures of the field sampling locations, documents the relationship between vapour space flammability and vapour pressure, and discusses the requirements for achieving gasoline-like flammability performance at high ethanol levels.