1,2,4,5-tetraoxane, mono and dinitrate glycerol carbonate ester derivatives of stearic acid were synthesized along with the known 9(10)-keto methyl sterate, methoxy mono-nitrate and dinitrate of methyl stearate. Their cetane numbers (CNs) were investigated to evaluate their viability for use as CN improvers. The CN performances of tetraoxane and all of the nitrate derivatives were investigated at 500 and 1000 ppm concentrations and compared to that of a traditional CN improver 2-ethylhexyl nitrate (2-EHN). The experimental results suggest that all derivatives evaluated in this study showed better CN improvement than base diesel fuel. Specifically, the 1,2,4,5-tetraoxane derivative of stearic methyl ester was superior to all derivatives studied, also being superior to 2-EHN. We also discussed the correlations between the observed CN trends and thermo-analytical data resulted from thermo gravimetric analysis curves (TGA) and differential scanning calorimetry (DSC).