Alkyl-substituted ferrocenes are typical burning-rate catalysts in composite solid propellants, but their high migration tendency and volatility has impeded their extensive applications. By introducing the concept of ionic energetic compounds, eight new ionic binuclear ferrocenyl compounds, [FcCH 2 N(CH 3 ) 2 (CH 2 ) n N(CH 3 ) 2 CH 2 Fc] 2+ (X – 2 ) (Fc = ferrocenyl; X – = 1,1,3,3-tetracyano propenide; n = 3–10; the compounds being numbered consecutively 1 – 8 ), were prepared and characterized. The molecular structures of 1 , 2 , and 4 were determined by single-crystal X-ray diffraction, and their cations were studied by density functional theory calculations (DFT). Compounds 1 – 5 show high thermal stability but 6 – 8 are slightly volatile. The results of cyclic voltammetry studies suggest that each salt exhibits a quasireversible redox system. Catalytic effects of the new salts on thermal degradation of ammonium perchlorate (AP), 1,3,5-trinitro-1,3,5-triaza-cyclo-hexane (RDX), and 1,2,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), have been investigated by DSC and/or TG methods. The results show that the new compounds can bring the peak temperatures of both AP and RDX down significantly and enhance their heat release dramatically, indicating that the ferrocenyl salts possess high catalytic efficiency for the thermal decomposition of AP and RDX. Their catalytic activities are nearly equal to or higher than that of the corresponding nitrates and picrates, as well as their mononuclear counterparts. Compound 6 also efficiently catalyzes the thermal decomposition of hydroxyl-terminated polybutadiene (HTPB) and 1:1 mixtures of HTPB and AP.