In order to explore the possibility of substituting nanothermite-explosive hybrid composites for primary explosive， nano-Al， nano-Bi₂O₃， raw HNIW and nano-HNIW were used to prepare Al/Bi₂O₃-HNIW by two methods： solvent-nonsolvent method （SN） and physical mixing method （PM）. The properties of Al/Bi₂O₃-HNIW were characterized and tested by scanning electron microscope （SEM）， X-ray diffractometer （XRD）， X-ray photoelectron spectroscopy （XPS）， closed bomb test and lead plate test. Results show that Al/Bi₂O₃ is uniformly coated on the surface of HNIW by SN. The optimal mass ratio of Al/Bi₂O₃ to HNIW for Al/Bi₂O₃-HNIW （SN） is 3∶7， with a high pressurization rate of 2.914 GPa·s^-1， which is triple of Al/Bi₂O₃-HNIW （PM），and the pressurization time is shorter. The electrostatic sensitivity of Al/Bi₂O₃-HNIW （SN） is significantly lower than lead styphnate and lead azide， and even PETN. Al/Bi₂O₃-HNIW（SN） can detonate RDX using PETN as intermediate charge. Al/Bi₂O₃-HNIW （SN） is expected to be used as a substitute for primary explosive for its excellent safety and initiation performance.