To retard high migration tendency of alkylferrocene-based burning rate catalysts and ameliorate their combustion catalytic activity, twenty new nitrogen-rich N-heterocyclic ferrocenyl compounds 1 - 20 were synthesized by click reaction and characterized by NMR, UV-Vis, FT-IR, ESI-MS, etc. Six compounds were structurally confirmed by single crystal X-ray diffraction additionally. TG studies showed that the new ferrocenyl compounds are highly thermal stable. Cyclic voltammetry results implied that some new ferrocenyl compounds exhibit reversible electrochemical behavior, which are favorable for their combustion catalytic performance in the composite solid propellants. The anti-migration tests confirmed that the new ferrocenyl compounds exhibit neglectable migration trends after four-week aging on comparison with ferrocene and catocene. The catalytic combustion tests of AP, RDX or HMX over the compounds 1 - 20 indicated that these N-heterocyclic ferrocenes are all highly active for improving thermal degradation of AP and RDX and more active than the aniline-derived counterparts prepared by click reaction.