Biodiesel as a typical green energy and having of environmental and economic values is therefore suitable for emulsion explosive. Herein, we have demonstrated the use of biodiesel as a partial substitute of composite wax of emulsion explosives (EE), and mainly focused on the effects of biodiesel content on the thermal safety and explosion characteristics of EE. Compared with the EE without biodiesel, the average particle size of the internal phase decreases by 45.66 %, and the activation energy of the thermal decomposition reaction increases by 44.90 % when the biodiesel substitution amount is 2 %. The detonation velocity and lead column compression ratio are 5185 m/s and 0.4219 respectively, which were almost consistent with the sample without biodiesel.It follows that biodiesel addition increased the thermal safety of emulsion explosive simultaneously guaranteed explosive performance. Consequently, biodiesel can be developed as a promising oil phase substitute for EE.