Ferrocene-based epoxy of the special chemical structure is composed of epoxy and ferrocene. These materials behave as structurally diverse monomers and multifunctional polymers. In recent years, more attention is focused on synthetic approaches and applications due to their high chemical activity and multifunctionality. More than twenty small molecules of ferrocene-based epoxy have been synthesized via ferrocenyl aldehydes, ketones, alkene, chlorohydrins, diols, or chloroacetyl intermediates, and polymerized derivatives have also been developed by ferrocene-modified epoxy polymers or free radical copolymerization of glycidyl ether and vinylferrocene. This review intends to offer relevant synthetic strategies for the preparation of covalent systems based on epoxy and ferrocene. Particular attention has been paid to understand the fundamental stability of these systems. The vicinal epoxy facilitates the formation of ferrocenyl carbonium ions, and is labile toward ring opening and consequent isomerization to the aldehyde. A variety of architectures have a wide range of potential applications in areas such as functional materials, biomedical mediators, chiral ferrocenyl ligands, burn-rate catalysts and antitumor agents, among others. Detailed examples with different chemical structures of polymers are provided to illustrate about their applications. Finally, the future development at the surface and interface of materials is prospected.