Alkyl-substituted ferrocenium salts have limited solubility in epoxy oligomers and produce poisonous arene by photolysis. Herein, the synthesis and photoactivity of several alkoxy-substituted ferrocenium salts as long-wavelength UV light photoinitiators have been reported. [Cyclopendadien-Fe-anisole]PF 6 , [Cyclopen-dadien-Fe-anisole]BF 4 , [Cyclopendadien-Fe-diphenylether]PF 6 , [Cyclopendadien-Fe-diphenylether]BF 4 , and [Cyclopendadien-Fe-diethoxybenzene] PF 6 for polymerization of epoxy resin were prepared through the ligand exchange reaction between one ring of ferrocene and aromatic ether. They all display good solubility and photoini-tiating activities in epoxy resins.