To tackle high-migratory and high-volatility problem of marketed neutral ferrocene-based burning rate catalysts, twenty-one ferrocene-based 1,2,3-triazolyl compounds (Fc-TAZs) were synthesized by click reaction and characterized completely by NMR, FT-IR, UV–Vis and elemental analysis. In addition, four compounds were structurally confirmed by single crystal X-ray diffraction. TG and DSC analysis showed that the new Fc-TAZs are of high thermal stability. Cyclic voltammetry investigations suggested that more than half of the Fc-TAZs are reversible redox systems. Anti-migration and anti-volatility tests revealed that all the Fc-TAZs display, on comparison with Catocene, extremely low volatility and migration tendency due to the appearance of polar oxygen and nitrogen atoms in their molecules. Catalytic activity tests of the novel Fc-TAZs towards the thermal decomposition of oxidizers, evaluated by TG and DSC techniques, indicated that all Fc-TAZs exert great effects on the thermal disintegration of AP and compounds 5, 7 and 11 can promote the thermal decomposition of HMX during combustion.