In this work, boron nitride nanoplates (BNNPs) supported nanoscale zero-valent iron (nZVI) was prepared through facile liquid-phase chemical reduction of ferric ion by borohydride under ambient conditions in the presence of BNNPs. The nZVI@BNNPs hybrids were characterized by scanning electron microscopy, X-ray diffraction and magnetic properties measurement. The hybrid material was evaluated for decolorization of a common azo dye, methyl orange (MO), with the assistance of ultrasonic irradiation. Results exhibited that a complete decolorization of 100 mg/L MO was achieved within 6 min using nZVI@BNNPs as the active material. Compared with bare nZVI and BNNPs, nZVI@BNNPs provided a faster reaction process for MO decolorization. The kinetic rate constants of MO decolorization reached 0.8175 min−1 under ultrasound-assisted condition due to the synergistic effect of ultrasonic irradiation. Fluorescence spectrum experiment confirmed that hydroxyl radicals could be generated in the system combined nZVI with ultrasonic irradiation, and as a result, hydroxyl radicals would contribute to the decolorization process of MO.