Hexabenzylhexaazaisowurtzitane (HBIW) is the precursor to hexanitrohexaazaisowurtzitane (HNIW)—the most powerful high energy density explosive ever tested. Improvement of quality and yield of HBIW is one of the measures to decrease the cost of HNIW. In this paper,a comparison of acetonitrile process with ethanol process for synthesis of HBIW is made from the points of yield,quality,reaction rate and reaction conditions based on experimental results. It′s undoubted that acetonitrile process is superior to ethanol process in all mentioned aspects. It should be considered that acetonitrile is more toxic than ethanol,but its toxicity is still moderate. Based on American codes,the values of LD₅₀,LC₅₀ and TLV-TWA of acetonitrile are higher than or comparable with those of acetic acid,acetic anhydride,N,N-dimethylformamide and chloroform etc. With adequate protection measures the safety of acetonitrile process will not be a problem. But emphasis must be put on safety when acetonitrile process is used.