The fire and explosion hazards for a mixture demonstrating minimum flash point behavior (MinFPB) are greater than for those of its individual components. Studies of MinFPB for ternary solutions are extremely rare, although such solutions are frequently encountered in real processes. A new type of MinFPB for ternary mixtures with three binary constituents showing MinFPB is reported in this study. This new type of MinFPB was observed in methyl butyrate + ethanol + octane and propyl acetate + ethanol + octane. The minimum flash point value for the two studied mixtures is not only lower than that of the individual components but was also lower than the minimum ones of the three constituent binary mixtures. Such an observation has not formerly been reported. This finding has implications for fuel design, hazard assessment, process safety design, and process safety operation.