In order to explore the effect of biodiesel on the thermal decomposition characteristics and vibration resistance of on-site mixed emulsion explosives， the microscopic structure， thermal decomposition characteristics and vibration resistance of the matrix samples of on-site mixed emulsion explosives with biodiesel as the oil phase material were studied by laser particle size analyzer， optical microscope， synchronous thermal analysis technology， vibration experiment and water dissolution method， in which the mass contents of biodiesel were 0%， 1%， 2% and 3%， respectively. The results show that the average particle size of the on-site mixed emulsion explosive matrix samples with biodiesel is smaller， the uniformity of the internal phase particles is better， and the average particle size and dispersion index are reduced by 12.9% and 38.0% respectively， compared with the sample without biodiesel. When the mass content of biodiesel in the sample is 3%， the initial temperature， peak temperature and activation energy of the decomposition reaction are reduced by 5.8%， 3.7% and 12.3%， respectively， compared with the in-situ mixed emulsion explosive matrix sample without biodiesel， indicating that the thermal stability is reduced. The anti-vibration performance of the on-site mixed emulsion explosive matrix sample with 3% biodiesel is the worst. The dissolution loss rate increases from 0.117% to 0.313% after 6 vibration periods， and the crystallization phenomenon appears after 4 vibration periods. The on-site mixed emulsion explosive matrix sample with 1% biodiesel has the best anti-vibration performance. After 6 vibration periods， the dissolution rate increases from 0.070% to 0.197%， and no crystallization occurs. When the content of biodiese is 1%， the average particle size of the internal phase is small， the distribution uniformity is good， the thermal safety is high and the vibration resistance is the best.