Thermal methods such as differential scanning calorimetry (DSC), and elemental analysis (EA) were employed to determine the calorific values of some renewable biofuels either directly or indirectly. The biofuels tested were the common milkweed, dogbane, kudzu, and eucalyptus tree. The purpose of this work was to optimize the experimental conditions for DSC analysis of biofuels, improve the calorific values by adding metal oxides as catalysts, and compare the heat values between DSC and EA analyses.