Abstract: Abstract: Biodiesel, as a renewable alternative fuel, is easily crystallized at low temperature, which limits the application of engines fueled with biodiesel. Biodiesel is mainly composed of methyl palmitate (C16:0), methyl stearate (C18:0) and methyl oleate (C18:1). The properties of fuel are closely related to the properties of its compositions, and the fuel properties will change with different mole fraction ratios of some composition. So, it is very important to research the thermal parameters of different compositions. Differential scanning calorimetry (DSC) is a thermo analytical technique by which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. The result of a DSC experiment is a curve of heat flux related to temperature or time. Through this curve, it is easy to determine transition temperatures and enthalpies, which makes DSC a valuable tool in producing phase diagrams for various chemical systems. Based on the differential scanning calorimeter, thermal parameters of the three methyl esters have been analyzed. The melting point and fusion enthalpy of saturated fatty acid esters (C16:0 and C18:0) are much higher than the ones of unsaturated fatty acid ester (C18:1), the melting points of C16:0, C18:0 and C18:1 are 301.57, 310.92 and 255.01 K, respectively. The binary solution of fatty acid methyl esters has also been scanned, where each curve exhibits two distinct exothermic peaks. These phenomena can be explained in that the high melting point saturated ester precipitated first and the low melting point unsaturated ester precipitated later. Moreover, the crystallization temperature of these solutions is lower than the melting point temperature of the pure saturated fatty acid esters, which precipitated earliest in the solution. It is also clear that the solution crystallization temperature rises accordingly, because the increase of the mass fraction of saturated fatty acid esters. Supposing that biodiesel is a solution combined with different fatty acid methyl esters, the saturated fatty acid esters C16:0 and C18:0 are treated as solutes and the unsaturated fatty acid ester C18:1 is played as solvent, thus the thermodynamic model for calculating the crystallization temperature of the solution has been established. While predicting the crystallization temperature, the solution of fatty acid esters has been dealt with further as an ideal solution; because it just looks at liquid composition as the ideal solution and solid phase composition as not mutually soluble, the model has been simplified. The crystallization temperature of the four different kinds of biodiesel has been calculated by this simplified model, and also has acquired effective verification as compared with the experimental data.