The purpose of this study is to investigate influences of tall oil biodiesel with Mg and Mo based fuel additives on diesel engine performance and emission. Tall oil resinic acids were reacted with MgO and MgO2 stoichiometrically for the production of metal-based fuel additives (combustion catalysts). The metal-based additives were added into tall oil biodiesel (1360) at the rate of 4 mu mol/l, 8 mu mol/l and 12 mu mol/l for preparing test fuels. In general, both of the metal-based additives improved flash point, pour point and viscosity of the biodiesel fuel, depending on the rate of additives. A single cylinder DI diesel engine was used in the tests. Engine performance values did not change significantly with biodiesel fuels, but exhaust emission profile was improved. CO emissions and smoke opacity decreased by 56.42% and by 30.43%, respectively. In general, low NO, and CO2 emissions were measured with the biodiesel fuels.