To investigate the effect of boron nitride (BN) content on the explosive performance of on-site mixed bulk emulsion explosives, transmission electron microscopy (TEM) and optical microscopy were employed to characterize the microstructure of BN particles and the matrix, respectively. Air blast testing, the probe method, and the lead cylinder compression test were used to determine the shock wave parameters, detonation velocity, and brisance of the BN-containing on-site mixed bulk emulsion explosives. Combined with theoretical calculations, the influence of BN content on the microstructure and explosive properties was systematically studied. The test results indicate that the addition of BN did not significantly affect the stability of the internal phase droplets. As the BN content increased from 0% to 1.6%, the detonation velocity, brisance, and peak overpressure all exhibited a trend of initial increase followed by decrease: the detonation velocity increased from 3850.45m·s⁻¹ to 4724.89m·s⁻¹ and then decreased to 3903.20m·s⁻¹, with a maximum increase of 22.71%; the brisance increased from 13.86 mm to 19.87mm and then decreased to 17.18mm, with a maximum increase of 43.36%; the peak overpressure increased from 136.44kPa to 318.33kPa and then decreased to 285.41kPa, with a maximum increase of 133.31%; the specific impulse increased from 9.23Pa·s to 33.98Pa·s and then decreased to 31.99Pa·s, with a maximum increase of 268.15%. Based on the experimental results, introducing an appropriate amount of BN can significantly enhance the explosive performance of on-site mixed bulk emulsion explosives.