Tris-(m-nitrophenyl) bismuthine and tris-p-nitrophenyl) bismuthine were synthesized by Grignard reaction and metal transfer method by using m-chloronitrobenzene,p-chloronitrobenzene and bismuthine chloride as raw materials. The melting point of two unreported energetic bismuth complexs is 76-77 ℃ and 91-92 ℃ respectively. The catalytic effect of curing solid propellant hydroxy-terminated polybutadiene (HTPB) was studied by DTA. The DTA curves for HTPB system added tris-(m-nitrophenyl) bismuthine showed an exothermic peak temperature at 120.2 ℃. The catalytic effect was identified to that as the room-temperature curing catalyst tris-(ethoxyphenyl) bismuthine (TEPB).