Hexanireobibenyl (HNBB) is an important intermediate of hexanitrostibene (HNS). And the low yield of HNBB is the primary influence factor of gross yield of HNS. Therefore, how to increase the yield of HNBB was investigated in the article. The relation between the pH value of sodium hypochlorous acid solution and the yield of HNBB was detailedly discussed in the coupled reaction. The molecule structure of HNBB have been determined by NMR and Mass spectrum. Furthermore, the sensitivity performance was researched.