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]PF6, [Cyclopendadien-Fe-anisole]BF4, [Cyclopendadien-Fe-diphenyledier]PF6, [Cyclopendadien-Fe-diphenylether]BF4, and [Cyclopendadien-Fe-diethoxybenzene] PF6 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 photoinitiating activities in epoxy resins.